Pipe Section Having Unbonded Composite Barrier Layer

ABSTRACT

Pipe sections and methods for forming pipe sections are disclosed. A pipe section includes a hollow body formed from a polymer material, the hollow body having an inner surface and an outer surface, the inner surface defining an interior. The pipe section further includes a barrier layer surrounding and unbonded from the hollow body, the barrier layer having an inner surface and an outer surface. The barrier layer is formed from a continuous fiber reinforced thermoplastic material. Such pipe sections may be lightweight and flexible while exhibiting improved strength characteristics.

CROSS REFERENCE TO RELATED APPLICATIONS

The present application claims filing benefit of U.S. Provisional Patent application 61/623,618 having a filing date of Apr. 13, 2012; U.S. Provisional Patent application 61/665,423 having a filing date of Jun. 28, 2012; U.S. Provisional Patent application 61/678,370 having a filing date of Aug. 1, 2012; U.S. Provisional Patent application 61/703,331 having a filing date of Sep. 20, 2012; U.S. Provisional Patent application 61/707,314 having a filing date of Sep. 28, 2012; U.S. Provisional Patent application 61/717,899 having a filing date of Oct. 24, 2012; and U.S. Provisional Patent application 61/739,926 having a filing date of Dec. 20, 2012, all of which are incorporated herein by reference in their entirety.

BACKGROUND OF THE INVENTION

Multi-layer pipe assemblies are commonly utilized to convey oil, gas, and/or other suitable fluids. In particular, such pipe assemblies are employed in the oil and gas industry, such as in subsea applications as well as in oil and gas production fields. In subsea applications, for, example, multi-layer pipes may be utilized in risers, transfer lines, umbilicals and/or other suitable pipe assemblies. In production field applications, multi-layer pipes may be utilized in risers, infield flow lines, export pipelines and/or other suitable pipe assemblies.

Multi-layer pipe assemblies, and the pipe sections thereof, typically include at least two layers; a hollow body or inner layer, and a barrier layer or outer layer generally surrounding the hollow body. Other layers may further be included generally surrounding the barrier layer. Various materials have been utilized to form each of these layers, in an effort to improve various performance characteristics of the resulting pipe sections. Additionally, in these layers have been bonded together or left unbonded, depending on the application and the desired performance of the pipe section. For example, U.S. Pat. No. 5,876,648 discloses a pipe section having a metal inner layer and an outer layer formed by particular shrinkable polymers. U.S. Pat. No. 6,039,083 discloses a pipe section having a metal inner layer and an outer layer formed by particular polymers. U.S. Pat. No. 8,210,212 discloses a pipe section having a metal inner layer and a polymer outer layer. U.S. Pat. No. 8,163,364 discloses a pipe section having a polymer layer and a film layer. U.S. Patent Application No. 2009/0301594 discloses a pipe section having a metal inner layer and an outer layer formed from a polyphenylene sulfide (PPS). U.S. Patent Application No. 2010/0326558 discloses a pipe section having an inner layer and a polymer outer layer. U.S. Patent Application No. 2011/0041947 discloses a pipe section having a thermoplastic inner layer and a tape outer layer bonded to the inner layer. Japanese Patent No. 3021435 discloses a pipe section having a thermoplastic inner layer and a tape outer layer.

However, the materials utilized in such known pipe assemblies do not provide the characteristics required for many applications. For example, in many cases, particularly when polymer hollow cores are utilized, the barrier layers remain unreinforced. Thus, the strength of the overall pipe section may be limited. In many cases, additional layers are added, surrounding the barrier layer, to strengthen the pipe section. However, such additional layers add weight to the pipe section and reduce the flexibility thereof.

Accordingly, improved pipe sections and assemblies formed from such pipe sections are desired in the art. In particular, pipe sections that utilized barrier layers which provide increased strength to the overall pipe section are desired. Lightweight pipe sections with increased strength and flexibility would be particularly advantageous.

SUMMARY OF THE INVENTION

In accordance with one embodiment of the present disclosure, a pipe section is disclosed. The pipe section includes a hollow body formed from a polymer material, the hollow body having an inner surface and an outer surface, the inner surface defining an interior. The pipe section further includes a barrier layer surrounding and unbonded from the hollow body, the barrier layer having an inner surface and an outer surface, the barrier layer formed from a continuous fiber reinforced thermoplastic material.

In accordance with another embodiment of the present disclosure, a method for forming a pipe section is disclosed. The method includes providing a hollow body formed from a polymer material, the hollow body having an inner surface and an outer surface, the inner surface defining an interior. The method further includes surrounding the hollow body with a barrier layer such that the barrier layer is in contact with and unbonded from the outer surface of the hollow body. The barrier layer is formed from a continuous fiber reinforced thermoplastic material.

Other features and aspects of the present invention are set forth in greater detail below.

BRIEF DESCRIPTION OF THE DRAWINGS

A full and enabling disclosure of the present invention, including the best mode thereof to one skilled in the art, is set forth more particularly in the remainder of the specification, including reference to the accompanying figures, in which:

FIG. 1 illustrates various pipe assemblies in a subsea application in accordance with one embodiment of the present disclosure;

FIG. 2 illustrates various pipe assemblies in a production field application in accordance with one embodiment of the present disclosure;

FIG. 3 is a perspective view of a multi-layer pipe section in accordance with one embodiment of the present disclosure;

FIG. 4 is a perspective view of multi-layer pipe section in accordance with another embodiment of the present disclosure;

FIG. 5 is a cross-sectional view of a multi-layer pipe section in accordance with another embodiment of the present disclosure;

FIG. 6 is a schematic representation of a process for forming a polyarylene sulfide composition in accordance with one embodiment of the present disclosure;

FIG. 7 is a schematic illustration of an impregnation system in accordance with one embodiment of the present disclosure;

FIG. 8 is a perspective view of a die in accordance with one embodiment of the present disclosure;

FIG. 9 is a cross-sectional view of the die shown in FIG. 8;

FIG. 10 is an exploded view of a manifold assembly and gate passage for a die in accordance with one embodiment of the present disclosure;

FIG. 11 is a perspective view of one embodiment of a second impregnation plate at least partially defining an impregnation zone in accordance with one embodiment of the present disclosure;

FIG. 12 is a close-up cross-sectional view of a portion of an impregnation zone in accordance with one embodiment of the present disclosure;

FIG. 13 is a close-up cross-sectional view of a downstream end portion of an impregnation zone in accordance with one embodiment of the present disclosure;

FIG. 14 is a perspective view of a land zone in accordance with one embodiment of the present disclosure;

FIG. 15 is a perspective view of a land zone in accordance with one embodiment of the present disclosure;

FIG. 16 is a perspective view of a tape in accordance with one embodiment of the present disclosure;

FIG. 17 is a cross-sectional view a tape in accordance with one embodiment of the present disclosure;

FIG. 18 illustrates the sample used in determination of melt strength and melt elongation of polyarylene sulfide compositions described herein.

FIG. 19 illustrates the effect of temperature change on the notched Charpy impact strength of a polyarylene sulfide composition as described herein and that of a comparison composition.

FIG. 20 is a scanning electron microscope image of a polyarylene sulfide composition as described herein (FIG. 20A) and a comparison polyarylene sulfide (FIG. 20B).

FIG. 21 compares the effect of sulfuric acid exposure on strength characteristics of polyarylene sulfide compositions as described herein and a comparison composition.

FIG. 22 provides the log of the complex viscosity obtained for polyarylene sulfide compositions described herein as a function of the shear rate.

FIG. 23 provides the melt strength of polyarylene sulfide compositions described herein as a function of the Hencky strain.

FIG. 24 provides the melt elongation for polyarylene sulfide compositions described herein as a function of Hencky strain.

FIG. 25 illustrates the daily weight loss for testing samples in determination of permeation resistance of polyarylene sulfide compositions to CE10 fuel blend.

FIG. 26 illustrates the daily weight loss for testing samples in determination of permeation resistance of polyarylene sulfide compositions to CM15A fuel blend.

FIG. 27 illustrates the daily weight loss for testing samples in determination of permeation resistance of polyarylene sulfide compositions to methanol.

Repeat use of reference characters in the present specification and drawings is intended to represent the same or analogous features or elements of the present invention.

DETAILED DESCRIPTION OF REPRESENTATIVE EMBODIMENTS

It is to be understood by one of ordinary skill in the art that the present discussion is a description of exemplary embodiments only, and is not intended as limiting the broader aspects of the present invention.

Generally speaking, the present disclosure is directed to pipe sections and methods for forming pipe sections. The resulting pipe sections may be utilized in a variety of applications and, in particular, in harsh environments, such as in oil and gas applications. Advantageously, the materials utilized to form pipe sections according to the present disclosure can be tailored for specific applications so as to withstand specific environments and the associated temperatures, pHs, abrasion, etc. Pipe sections formed according to the present disclosure are advantageously lightweight and exhibit flexibility in addition to high strength and resistance properties.

As discussed in detail below, the innermost layer, or hollow core, of a multi-layer pipe section formed according to the present disclosure may be formed from a polymer material, which in exemplary embodiments is a thermoplastic. The inner core may be exposed to relatively harsh environments, such as oil, gas, or other fluids or slurries being flowed therethrough. Use of a polymer material to form the hollow core provides the hollow core with improved resistance properties, such as resistance to wear and corrosion. Further, the hollow core may advantageously be lightweight. A barrier layer surrounding and in contact with the hollow core may be formed from a continuous fiber reinforced thermoplastic (“CFRT”) material. This barrier layer and hollow core may further advantageously be unbonded. Use of a reinforced barrier layer that is unbonded may increase the overall flexibility of the pipe section, while additionally increasing the strength of the overall pipe section, in particular the burst pressure resistance and tensile strength thereof.

Accordingly, a pipe section according to the present disclosure thus includes a polymer hollow body and one or more CFRT barrier layers surrounding the hollow body. The barrier layers may be unbonded from the hollow body. Further, in exemplary embodiments, the barrier layer is a tape formed from the CFRT material. The use of unbonded barrier layers formed from CFRT material may impart numerous advantages to the pipe sections formed therefrom. In particular, such pipe sections may be lightweight and flexible while exhibiting improved strength characteristics.

In some embodiments, a pipe section formed according to the present disclosure may be utilized in an oil and gas application. For example, in subsea applications, a pipe section formed according to the present disclosure may be utilized in a riser, transfer line, umbilical or other suitable subsea pipe assembly. Risers, transfer lines, etc. may flow oil or gas therethrough. Umbilicals may include various elements for transferring fluids and/or electric current/signals. For example, an umbilical may contain elongated umbilical elements (e.g., two or more), such as a channel element, fluid pipe, electric conductor/wire (e.g., optic fiber cable), armoring wire, etc. The pipe section may enclose these elements. In production field applications, pipe sections formed according to the present disclosure may be utilized in risers, infield flow lines, export pipelines and/or other suitable pipe assemblies.

FIG. 1 illustrates one embodiment of a subsea pipe system 10, which is one application in which pipe sections formed according to the present disclosure may be utilized. The pipe system 10 may include one or more pipe sections 100, and extends between a subsea facility 14, such as a well bore, and a vessel 16, such as a drilling rig, ship, etc., or between two vessels 16, or otherwise. The subsea facility 14 may be adjacent to the bottom 20 of a body of water 22. The vessel 16 and/or subsea facility 14 may be permanently installed or movable within the body of water 22. In certain embodiments, the subsea pipe system 10 may be employed in water having a depth of about 2,500 meters or more, in some embodiments about 4,000 meters or more, and in some embodiments, from about 5,000 to about 15,000 meters. The subsea pipe system 900 may span significant portions of these depths.

In exemplary embodiments, a subsea pipe system 10 is utilized to transport a liquid, such as oil, or a gas between the subsea facility 14 and the vessel 16, or to contain various elements therein. The pipe system 10 may thus include, for example, a riser 24, a transport line 26, an umbilical, or any other suitable pipe for such applications. A pipe section 100 according to the present disclosure may be utilized to form any one or more of these pipe assemblies.

FIG. 2 illustrates a typical production field that can incorporate a pipe section according to the present disclosure in various pipe assemblies. As can be seen, the field can include fixed risers 31 that can carry production fluid from the sea floor 32 to a platform 35. The field can include infield flowlines 33 that can carry production fluid, supporting fluids, umbilicals, etc., within the field. In addition, both the risers 31 and the infield flowlines 33 can be bundled lines as discussed above. The system also includes a plurality of tie-ins 34 at which point different flowlines can be merged, for instance to form a bundled riser and/or where individual flowlines may be altered, for instance through expansion. The system also includes a plurality of satellite wells 38 from which the hydrocarbon production fluid is obtained and manifolds. An export pipeline 37 can carry production fluid from the platform 35 to shore, a storage facility, or a transport vessel. The export pipeline 37 may also include one or more crossings 36 to by-pass other flowlines, e.g., another pipeline 39. A pipe section 100 according to the present disclosure may be utilized to form any one or more of these pipe assemblies

FIGS. 3 through 5 illustrate pipe sections 100 according to various embodiments of the present disclosure. A pipe section 100 includes a hollow body 102. The hollow body 102 has an inner surface 104 and an outer surface 106, as shown. The inner surface 104 defines an interior 108 of the hollow body 102, through which a suitable material, such as a liquid or gas as discussed above, may flow. The hollow body 102 may in exemplary embodiments be generally cylindrical, having a circular or oval-shaped cross-sectional profile. Alternatively, the hollow body 102 may have any suitable shape, which may be constant or may vary. The hollow body 102 may extend along a longitudinal axis 110. It should be noted that the longitudinal direction 110 is a direction generally through the center of the hollow body 102, and may correspond for example to a flow direction through the hollow body 102. Thus, the longitudinal direction 110 may curve at any suitable angle as required based on the curvature of the hollow body 102.

The hollow body 102 may be formed from a suitable polymer material, which in exemplary embodiments may be a thermoplastic material but alternatively may be a thermoset material. For example, other suitable thermoplastic polymers for use in the hollow body 102 may include, for instance, polyolefins (e.g., polypropylene, propylene-ethylene copolymers, etc.), polyesters (e.g., polybutylene terephalate (“PBT”)), polycarbonates, polyamides (e.g., PA12, Nylon™), polyether ketones (e.g., polyether ether ketone (“PEEK”)), polyetherimides, polyarylene ketones (e.g., polyphenylene diketone (“PPDK”)), liquid crystal polymers, polyarylene sulfides (e.g., polyphenylene sulfide (“PPS”), poly(biphenylene sulfide ketone), poly(phenylene sulfide diketone), poly(biphenylene sulfide), etc.), fluoropolymers (e.g., polytetrafluoroethylene-perfluoromethylvinylether polymer, perfluoro-alkoxyalkane polymer, petrafluoroethylene polymer, ethylene-tetrafluoroethylene polymer, etc.), polyacetals, polyurethanes, polycarbonates, styrenic polymers (e.g., acrylonitrile butadiene styrene (“ABS”)), and so forth.

In exemplary embodiments, the polymer material may be extruded to form the hollow body 102, as shown in FIGS. 4 and 5. Alternatively, the hollow body 102 may be formed from a tape of the polymer material, as shown in FIG. 3, or have any other suitable formation.

A pipe section 102 according to the present disclosure further includes one or more barrier layers 120. Each barrier layer 120 may generally surround the hollow body 102. The innermost barrier layer 120 (relative to the hollow body 102) may be in contact with the hollow body 102, and surrounding outer barrier layers 120 may each be in contact with the neighboring barrier layer 120, as shown for example in FIG. 4. A barrier layer 120 has an inner surface 122 and an outer surface 124. When the innermost barrier layer 120 surrounds the hollow body 102, the inner surface 122 may contact the hollow body 102, such as the outer surface 106 thereof.

The barrier layer 120 may be unbonded from the hollow body 102. However, in some embodiments wherein more than one barrier layer 120 is utilized, these barrier layers 120 may bonded to each other. Bonding of the barrier layers 120 may involve heating the barrier layers 120 to consolidation temperatures. Heating may be performed in a die, heater, or otherwise during formation of a barrier layer 120 or tape thereof, or may be separately performed. A suitable heating source may be, for example, infrared, hot gas, laser, or otherwise. A consolidation temperature is a temperature that allows the neighboring barrier layers 120 to consolidate and thus be bonded together. For example, the consolidation temperature for a particular polymer resin may be the melting point temperature, or a temperature between approximately 20° C., 15° C., 10° C., or 5° C. below the melting point temperature and the melting point temperature for that polymer resin. Bonding may further include consolidating the barrier layers 120 together. Consolidation may involve, for example, pressing the barrier layers 120 together, or simply allowing the barrier layers 120 to remain in contact, after heating thereof. Bonding may further include cooling the barrier layers 120 after consolidation, and thus bonding thereof.

As discussed above and in detail below, a barrier layer 120 according to the present disclosure is formed from a continuous fiber reinforced thermoplastic material. Suitable thermoplastic materials for use in barrier layers 120 according to the present disclosure include, for instance, polyolefins (e.g., polypropylene, propylene-ethylene copolymers, etc.), polyesters (e.g., polybutylene terephalate (“PBT”)), polycarbonates, polyamides (e.g., PA12, Nylon™), polyether ketones (e.g., polyether ether ketone (“PEEK”)), polyetherimides, polyarylene ketones (e.g., polyphenylene diketone (“PPDK”)), liquid crystal polymers, polyarylene sulfides (e.g., polyphenylene sulfide (“PPS”), poly(biphenylene sulfide ketone), poly(phenylene sulfide diketone), poly(biphenylene sulfide), etc.), fluoropolymers (e.g., polytetrafluoroethylene-perfluoromethylvinylether polymer, perfluoro-alkoxyalkane polymer, petrafluoroethylene polymer, ethylene-tetrafluoroethylene polymer, etc.), polyacetals, polyurethanes, polycarbonates, styrenic polymers (e.g., acrylonitrile butadiene styrene (“ABS”)), and so forth.

The thermoplastic material utilized to form a barrier layer 120 according to the present disclosure may further include a plurality of fibers embedded therein to reinforce the thermoplastic material. In exemplary embodiments, the barrier layer 120 includes a plurality of continuous fibers, although it should be understood that long fibers may additionally be included therein. The fibers may be dispersed in the thermoplastic material forming the barrier layer 120. As used therein, the term “long fibers” generally refers to fibers, filaments, yarns, or rovings that are not continuous, and as opposed to “continuous fibers” which generally refer to fibers, filaments, yarns, or rovings having a length that is generally limited only by the length of a part. The fibers dispersed in the polymer material to form the barrier layer 120 may be formed from any conventional material known in the art, such as metal fibers, glass fibers (e.g., E-glass, A-glass, C-glass, D-glass, AR-glass, R-glass, S-glass such as S1-glass or S2-glass), carbon fibers (e.g., graphite), boron fibers, ceramic fibers (e.g., alumina or silica), aramid fibers (e.g., Kevlar® marketed by E. I. duPont de Nemours, Wilmington, Del.), synthetic organic fibers (e.g., polyamide, polyethylene, paraphenylene, terephthalamide, polyethylene terephthalate and polyphenylene sulfide), and various other natural or synthetic inorganic or organic fibrous materials known for reinforcing polymer compositions. Glass fibers, carbon fibers, and aramid fibers are particularly desirable.

In exemplary embodiments, the continuous fibers may be generally unidirectional, as shown in FIG. 16. Further, in exemplary embodiments, the barrier layer 120 is a tape formed from the CFRT material. In other embodiments, the barrier layer 120 may, for example, be extruded over the hollow body 102.

In some exemplary embodiments, a barrier layer 120 may be formed from a polyarylene sulfide composition that exhibits excellent strength and flexibility characteristics as well as resistance to chemical degradation due to contact with, e.g., water, oils, gas, synthetic or natural chemicals, etc. Beneficially, the polyarylene sulfide composition can maintain good physical characteristics even when utilized in extreme temperature applications such as high temperatures and low temperatures as may be encountered in piping applications. The polyarylene sulfide can also maintain good physical characteristics under conditions in which the materials are subjected to extreme temperature fluctuations.

The polyarylene sulfide compositions according to the present disclosure can be formed according to a melt processing technique that includes combining a polyarylene sulfide with an impact modifier to form a mixture and subjecting the mixture to dynamic vulcanization. More specifically, the polyarylene sulfide can be combined with the impact modifier and this mixture can be subjected to shear conditions such that the impact modifier becomes well distributed throughout the polyarylene sulfide. Following formation of the mixture, a polyfunctional crosslinking agent can be added. The polyfunctional crosslinking agent can react with the components of the mixture to form crosslinks in the composition, for instance within and between the polymer chains of the impact modifier.

Without being bound to any particular theory, it is believed that by adding the polyfunctional crosslinking agent to the polyarylene sulfide composition following distribution of the impact modifier throughout the polyarylene sulfide, interaction between the polyarylene sulfide, the impact modifier, and the crosslinking agent within the melt processing unit can be improved, leading to improved distribution of the crosslinked impact modifier throughout the composition. The improved distribution of the crosslinked impact modifier throughout the composition can improve the strength and flexibility characteristics of the composition, e.g., the ability of the composition to maintain strength under deformation, as well as provide a composition with good processibility that can be utilized to form a product that can exhibit excellent resistance to degradation under a variety of conditions.

According to one embodiment, a formation process can include functionalization of the polyarylene sulfide. This embodiment can provide additional sites for bonding between the impact modifier and the polyarylene sulfide, which can further improve distribution of the impact modifier throughout the polyarylene sulfide and further prevent phase separation. Moreover, functionalization of the polyarylene sulfide can include scission of the polyarylene sulfide chain, which can decrease the melt viscosity of the composition and improve processibility. This can also provide a polyarylene sulfide composition that is a low halogen, e.g., low chlorine composition that exhibits excellent physical characteristics and high resistance to degradation.

To provide further improvements to the polyarylene sulfide composition, the composition can be formed to include other conventional additives such as fillers, lubricants, colorants, etc. according to standard practice.

The high strength and flexibility characteristics of the polyarylene sulfide composition can be evident by examination of the tensile, flexural, and/or impact properties of the materials. For example, the polyarylene sulfide composition can have a notched Charpy impact strength of greater than about 3 kJ/m², greater than about 3.5 kJ/m², greater than about 5 kJ/m², greater than about 10 kJ/m², greater than about 15 kJ/m², greater than about 30 kJ/m², greater than about 33 kJ/m², greater than about 40 kJ/m², greater than about 45 kJ/m², or greater than about 50 kJ/m² as determined according to ISO Test No. 179-1 (technically equivalent to ASTM D256, Method B) at 23° C. The unnotched Charpy samples do not break under testing conditions of ISO Test No. 180 at 23° C. (technically equivalent to ASTM D256).

Beneficially, the polyarylene sulfide composition can maintain good physical characteristics even at extreme temperatures, including both high and low temperatures. For instance, the polyarylene sulfide composition can have a notched Charpy impact strength of greater than about 8 kJ/m², greater than about 9 kJ/m², greater than about 10 kJ/m², greater than about 14 kJ/m², greater than about 15 kJ/m², greater than about 18 kJ/m², or greater than about 20 kJ/m² as determined according to ISO Test No. 179-1 at −30° C.; and can have a notched Charpy impact strength of greater than about 8 kJ/m², greater than about 9 kJ/m², greater than about 10 kJ/m², greater than about 11 kJ/m², greater than about 12 kJ/m², or greater than about 15 kJ/m² as determined according to ISO Test No. 179-1 at −40° C.

Moreover, the effect of temperature change on the polyarylene sulfide composition can be surprisingly small. For instance, the ratio of the notched Charpy impact strength as determined according to ISO Test No. 179-1 at 23° C. to that at −30° C. can be greater than about 3.5, greater than about 3.6, or greater than about 3.7. Thus, and as described in more detail in the example section below, as the temperature increases the impact strength of the polyarylene sulfide composition also increases, as expected, but the rate of increase of the impact strength is very high, particularly as compared to a composition that does not include the dynamically crosslinked impact modifier. Accordingly, the polyarylene sulfide composition can exhibit excellent strength characteristics at a wide range of temperatures.

The polyarylene sulfide composition can exhibit very good tensile characteristics. For example, the polyarylene sulfide composition can have a tensile elongation at yield of greater than about 4.5%, greater than about 6%, greater than about 7%, greater than about 10%, greater than about 25%, greater than about 35%, greater than about 50%, greater than about 70%, greater than about 75%, greater than about 80%, or greater than about 90%. Similarly, the tensile elongation at break can be quite high, for instance greater than about 10%, greater than about 25%, greater than about 35%, greater than about 50%, greater than about 70%, greater than about 75%, greater than about 80%, or greater than about 90%. The strain at break can be greater than about 5%, greater than about 15%, greater than about 20%, or greater than about 25%. For instance the strain at break can be about 90%. The yield strain can likewise be high, for instance greater than about 5%, greater than about 15%, greater than about 20%, or greater than about 25%. The yield stress can be, for example, greater than about 50% or greater than about 53%. The polyarylene sulfide composition may have a tensile strength at break of greater than about 30 MPa, greater than about 35 MPa, greater than about 40 MPa, greater than about 45 MPa, or greater than about 70 MPa.

In addition, the polyarylene sulfide composition can have a relatively low tensile modulus. For instance, the polyarylene sulfide composition can have a tensile modulus less than about 3000 MPa, less than about 2300 MPa, less than about 2000 MPa, less than about 1500 MPa, or less than about 1100 MPa as determined according to ISO Test No. 527 at a temperature of 23° C. and a test speed of 5 mm/min.

The polyarylene sulfide composition can exhibit good characteristics after annealing as well. For instance, following annealing at a temperature of about 230° C. for a period of time of about 2 hours, the tensile modulus of the composition can be less than about 2500 MPa, less than about 2300 MPa, or less than about 2250 MPa. The tensile strength at break after annealing can be greater than about 50 MPa, or greater than about 55 MPa, as measured according to ISO Test No. 527 at a temperature of 23° C. and a test speed of 5 mm/min.

The polyarylene sulfide composition can also be utilized continuously at high temperature, for instance at a continuous use temperature of up to about 150° C., about 160° C., or about 165° C. without loss of tensile strength. For example, the polyarylene sulfide composition can maintain greater than about 95%, for instance about 100% of the original tensile strength after 1000 hours of heat aging at 165° C. and can maintain greater than about 95%, for instance about 100% of the original tensile elongation at yield after 1000 hours heat aging at 135° C.

Tensile characteristics can be determined according to ISO Test No. 527 at a temperature of 23° C. and a test speed of 5 mm/min or 50 mm/min (technically equivalent to ASTM D623 at 23° C.).

The flexural characteristics of the composition can be determined according to ISO Test No. 178 (technically equivalent to ASTM D790 at a temperature of 23° C. and a testing speed of 2 mm/min. For example, the flexural modulus of the composition can be less than about 2500 MPa, less than about 2300 MPa, less than about 2000 MPa, less than about 1800 MPa, or less than about 1500 MPa. The polyarylene sulfide composition may have a flexural strength at break of greater than about 30 MPa, greater than about 35 MPa, greater than about 40 MPa, greater than about 45 MPa, or greater than about 70 MPa.

The deflection temperature under load of the polyarylene sulfide composition can be relatively high. For example, the deflection temperature under load of the polyarylene sulfide composition can be greater than about 80° C., greater than about 90° C., greater than about 100° C., or greater than about 105° C., as determined according to ISO Test No. 75-2 (technically equivalent to ASTM D790) at 1.8 MPa.

The Vicat softening point can be greater than about 200° C. or greater than about 250° C., for instance about 270° C. as determined according to the Vicat A test when a load of 10 N is used at a heating rate of 50 K/hr. For the Vicat B test, when a load of 50 N is used at a heating rate of 50 K/hr, the Vicat softening point can be greater than about 100° C., greater than about 150° C. greater than about 175° C., or greater than about 190° C., for instance about 200° C. The Vicat softening point can be determined according to ISO Test No. 306 (technically equivalent to ASTM D1525).

The polyarylene sulfide composition can also exhibit excellent stability during long term exposure to harsh environmental conditions. For instance, under long term exposure to an acidic environment, the polyarylene sulfide composition can exhibit little loss in strength characteristics. For instance, following 500 hours exposure to a strong acid (e.g., a solution of about 5% or more strong acid such as sulfuric acid, hydrochloric acid, nitric acid, perchloric acid, etc.), the polyarylene sulfide composition can exhibit a loss in Charpy notched impact strength of less than about 17%, or less than about 16% following exposure of about 500 hours to a strong acid solution at a temperature of about 40° C., and can exhibit a loss in Charpy notched impact strength of less than about 25%, or less than about 22% following exposure of about 500 hours to a strong acid solution at a temperature of about 80° C. Even under harsher conditions, for instance in a 10% sulfuric acid solution held at a temperature of about 80° C. for 1000 hours, the polyarylene sulfide composition can maintain about 80% or more of the initial Charpy notched impact strength. The polyarylene sulfide composition can also maintain desirable strength characteristics following exposure to other potentially degrading materials, such as salts.

Permeation resistance can be important for a wide variety of applications for the polyarylene sulfide composition, for instance when utilizing the composition in formation of fuel lines, storage tanks, or the like. The polyarylene sulfide composition can exhibit excellent permeation resistance to a wide variety of materials. For instance, a shaped product formed of the polyarylene sulfide composition can exhibit a permeation resistance to a fuel or a fuel source (e.g., gasoline, diesel fuel, jet fuel, unrefined or refined oil, etc.) of less than about 3 g-mm/m²-day, less than about 2 g-mm/m²-day, less than about 1 g-mm/m²-day, or less than about 0.5 g-mm/m²-day. By way of example, the polyarylene sulfide composition (or a product formed of the polyarylene sulfide composition) can exhibit a permeation resistance to an ethanol blend of ethanol/iso-octane/toluene at a weight ratio of 10:45:45 at 40° C. of less than about 3 g-mm/m²-day, less than about 2.5 g-mm/m²-day, less than about 1 g-mm/m²-day, or less than about 0.1 g-mm/m²-day. The permeation resistance to a blend of 15 wt. % methanol and 85 wt. % oxygenated fuel (CM15A) at 40° C. can be less than about 3 g-mm/m²-day, less than about 2.5 g-mm/m²-day, less than about 1 g-mm/m²-day, less than about 0.5 g-mm/m²-day, less than about 0.3 g-mm/m²-day, or less than about 0.15 g-mm/m²-day. The permeation resistance to methanol at 40° C. can be less than about 1 g-mm/m²-day, less than about 0.5 g-mm/m²-day, less than about 0.25 g-mm/m²-day, less than about 0.1 g-mm/m²-day, or less than about 0.06 g-mm/m²-day. Permeation resistance can be determined according to SAE Testing Method No. J2665. In addition, the polyarylene sulfide composition can maintain original density following long term exposure to hydrocarbons. For example, the composition can maintain greater than about 95% of original density, greater than about 96% of original density, such as about 99% of original density following long term (e.g., greater than about 14 days) exposure to hydrocarbons such as heptane, cyclohexane, toluene, and so forth, or combinations of hydrocarbons.

The polyarylene sulfide composition can also be resistant to uptake of materials, and specifically hydrocarbons. For example, a molded structure formed of the composition can exhibit a volume change of less than about 25%, less than about 20%, or less than about 14% following exposure to the hydrocarbon at a temperature of 130° C. for a period of time of about two weeks.

The polyarylene sulfide composition can exhibit good heat resistance and flame retardant characteristics. For instance, the composition can meet the V-0 flammability standard at a thickness of 0.2 millimeters. The flame retarding efficacy may be determined according to the UL 94 Vertical Burn Test procedure of the “Test for Flammability of Plastic Materials for Parts in Devices and Appliances”, 5th Edition, Oct. 29, 1996. The ratings according to the UL 94 test are listed in the following table:

Afterflame Time Burn Rating (s) Burning Drips to Clamp V-0 <10 No No V-1 <30 No No V-2 <30 Yes No Fail <30 Yes Fail >30 No

The “afterflame time” is an average value determined by dividing the total afterflame time (an aggregate value of all samples tested) by the number of samples. The total afterflame time is the sum of the time (in seconds) that all the samples remained ignited after two separate applications of a flame as described in the UL-94 VTM test. Shorter time periods indicate better flame resistance, i.e., the flame went out faster. For a V-0 rating, the total afterflame time for five (5) samples, each having two applications of flame, must not exceed 50 seconds. Using the flame retardant of the present invention, articles may achieve at least a V-1 rating, and typically a V-0 rating, for specimens having a thickness of 0.2 millimeters.

The polyarylene sulfide composition can also exhibit good processing characteristics, for instance as demonstrated by the melt viscosity of the composition. For instance, the polyarylene sulfide composition can have a melt viscosity of less than about 2800 poise as measured on a capillary rheometer at 316° C. and 400 sec⁻¹ with the viscosity measurement taken after five minutes of constant shear. Moreover, the polyarylene sulfide composition can exhibit improved melt stability over time as compared to polyarylene sulfide compositions that do not include crosslinked impact modifiers. Polyarylene sulfide compositions that do not include a crosslinked impact modifier tend to exhibit an increase in melt viscosity over time, and in contrast, disclosed compositions can maintain or even decrease in melt viscosity over time.

The polyarylene sulfide composition can have a complex viscosity as determined at low shear (0.1 radians per second (rad/s)) and 310° C. of greater than about 10 kPa/sec, greater than about 25 kPa/sec, greater than about 40 kPa/sec, greater than about 50 kPa/sec, greater than about 75 kPa/sec, greater than about 200 kPa/sec, greater than about 250 kPa/sec, greater than about 300 kPa/sec, greater than about 350 kPa/sec, greater than about 400 kPa/sec, or greater than about 450 kPa/sec. Higher value for complex viscosity at low shear is indicative of the crosslinked structure of the composition and the higher melt strength of the polyarylene sulfide composition. In addition, the polyarylene sulfide composition can exhibit high shear sensitivity, which indicates excellent characteristics for use in formation processes such as blow molding and extrusion processing.

FIG. 6 illustrates a schematic of a process that can be used in forming the polyarylene sulfide composition. As illustrated, the components of the polyarylene sulfide composition may be melt-kneaded in a melt processing unit such as an extruder 700. Extruder 700 can be any extruder as is known in the art including, without limitation, a single, twin, or multi-screw extruder, a co-rotating or counter rotating extruder, an intermeshing or non-intermeshing extruder, and so forth. In one embodiment, the composition may be melt processed in an extruder 700 that includes multiple zones or barrels. In the illustrated embodiment, extruder 700 includes 10 barrels numbered 721-730 along the length of the extruder 700, as shown. Each barrel 721-730 can include feed lines 714, 716, vents 712, temperature controls, etc. that can be independently operated. A general purpose screw design can be used to melt process the polyarylene composition. By way of example, a polyarylene sulfide composition may be melt mixed using a twin screw extruder such as a Coperion co-rotating fully intermeshing twin screw extruder.

In forming a polyarylene sulfide composition, the polyarylene sulfide can be fed to the extruder 700 at a main feed throat 714. For instance, the polyarylene sulfide may be fed to the main feed throat 714 at the first barrel 721 by means of a metering feeder. The polyarylene sulfide can be melted and mixed with the other components of the composition as it progresses through the extruder 700. The impact modifier can be added to the composition in conjunction with the polyarylene sulfide composition at the main feed throat 714 or downstream of the main feed throat, as desired.

At a point downstream of the main feed throat 714, and following addition of the impact modifier to the composition, the crosslinking agent can be added to the composition. For instance, in the illustrated embodiment, a second feed line 716 at barrel 726 can be utilized for addition of the crosslinking agent. The point of addition for the crosslinking agent is not particularly limited. However, the crosslinking agent can be added to the composition at a point after the polyarylene sulfide has been mixed with the impact modifier under shear such that the impact modifier is well distributed throughout the polyarylene sulfide. Beneficially, the polyarylene sulfide composition can exhibit desirable characteristics without the addition of plasticizers. For instance, the composition can be free of plasticizers such as phthalate esters, trimellitates, sebacates, adipates, gluterates, azelates, maleates, benzoates, and so forth.

The polyarylene sulfide may be a polyarylene thioether containing repeat units of the formula (I):

—[(Ar¹)_(n)—X]_(m)—[(Ar²)_(i)—Y]_(j)—[(Ar³)_(k)—Z]_(l)—[(Ar⁴)_(o)—W]_(p)—  (I)

wherein Ar¹, Ar², Ar³, and Ar⁴ are the same or different and are arylene units of 6 to 18 carbon atoms; W, X, Y, and Z are the same or different and are bivalent linking groups selected from —SO₂—, —S—, —SO—, —CO—, —O—, —COO— or alkylene or alkylidene groups of 1 to 6 carbon atoms and wherein at least one of the linking groups is —S—; and n, m, i, j, k, l, o, and p are independently zero or 1, 2, 3, or 4, subject to the proviso that their sum total is not less than 2. The arylene units Ar¹, Ar², Ar³, and Ar⁴ may be selectively substituted or unsubstituted. Advantageous arylene systems are phenylene, biphenylene, naphthylene, anthracene and phenanthrene. The polyarylene sulfide typically includes more than about 30 mol %, more than about 50 mol %, or more than about 70 mol % arylene sulfide (—S—) units. In one embodiment the polyarylene sulfide includes at least 85 mol % sulfide linkages attached directly to two aromatic rings.

In one embodiment, the polyarylene sulfide is a polyphenylene sulfide, defined herein as containing the phenylene sulfide structure —(C₆H₄—S)_(n)— (wherein n is an integer of 1 or more) as a component thereof.

The polyarylene sulfide may be synthesized prior to forming the polyarylene sulfide composition, though this is not a requirement of a process, and a polyarylene sulfide can also be purchased from known suppliers. For instance Fortron® polyphenylene sulfide available from Ticona of Florence, Ky., USA can be purchased and utilized as the polyarylene sulfide. In those embodiments in which the polyarylene sulfide is synthesized, synthesis techniques as are generally known in the art may be used. By way of example, a process for producing a polyarylene sulfide can include reacting a material that provides a hydrosulfide ion, e.g., an alkali metal sulfide, with a dihaloaromatic compound in an organic amide solvent.

The polyarylene sulfide may be linear, semi-linear, branched or crosslinked. A linear polyarylene sulfide includes as the main constituting unit the repeating unit of —(Ar—S) —. In general, a linear polyarylene sulfide may include about 80 mol % or more of this repeating unit. A linear polyarylene sulfide may include a small amount of a branching unit or a cross-linking unit, but the amount of branching or cross-linking units may be less than about 1 mol % of the total monomer units of the polyarylene sulfide. A linear polyarylene sulfide polymer may be a random copolymer or a block copolymer containing the above-mentioned repeating unit.

A semi-linear polyarylene sulfide may be utilized that may have a cross-linking structure or a branched structure provided by introducing into the polymer a small amount of one or more monomers having three or more reactive functional groups. For instance between about 1 mol % and about 10 mol % of the polymer may be formed from monomers having three or more reactive functional groups. Methods that may be used in making semi-linear polyarylene sulfide are generally known in the art.

The polyarylene sulfide composition may include the polyarylene sulfide component (which also encompasses a blend of polyarylene sulfides) in an amount from about 10 wt. % to about 99 wt. % by weight of the composition, for instance from about 20% wt. % to about 90 wt. % by weight of the composition.

The polyarylene sulfide may be of any suitable molecular weight and melt viscosity, generally depending upon the final application intended for the polyarylene sulfide composition. For instance, the melt viscosity of the polyarylene sulfide may be a low viscosity polyarylene sulfide, having a melt viscosity of less than about 500 poise, a medium viscosity polyarylene sulfide, having a melt viscosity of between about 500 poise and about 1500 poise, or a high melt viscosity polyarylene sulfide, having a melt viscosity of greater than about 1,500 poise, as determined in accordance with ISO Test No. 11443 at a shear rate of 1200 s⁻¹ and at a temperature of 310° C.

According to one embodiment, the polyarylene sulfide can be functionalized to further encourage bond formation between the polyarylene sulfide and the impact modifier. For instance, a polyarylene sulfide can be further treated following formation with a carboxyl, acid anhydride, amine, isocyanate or other functional group-containing modifying compound to provide a functional terminal group on the polyarylene sulfide. By way of example, a polyarylene sulfide can be reacted with a modifying compound containing a mercapto group or a disulfide group and also containing a reactive functional group. In one embodiment, the polyarylene sulfide can be reacted with the modifying compound in an organic solvent. In another embodiment, the polyarylene sulfide can be reacted with the modifying compound in the molten state.

In one embodiment, a disulfide compound containing the desired functional group can be incorporated into the polyarylene sulfide composition formation process, and the polyarylene sulfide can be functionalized in conjunction with formation of the composition. For instance, a disulfide compound containing the desired reactive functional groups can be added to the melt extruder in conjunction with the polyarylene sulfide or at any other point prior to or in conjunction with the addition of the crosslinking agent.

Reaction between the polyarylene sulfide polymer and the reactively functionalized disulfide compound can include chain scission of the polyarylene sulfide polymer that can decrease melt viscosity of the polyarylene sulfide. In one embodiment, a higher melt viscosity polyarylene sulfide having low halogen content can be utilized as a starting polymer. Following reactive functionalization of the polyarylene sulfide polymer by use of a functional disulfide compound, a relatively low melt viscosity polyarylene sulfide with low halogen content can be formed. Following this chain scission, the melt viscosity of the polyarylene sulfide can be suitable for further processing, and the overall halogen content of the low melt viscosity polyarylene sulfide can be quite low. A polyarylene sulfide composition that exhibits excellent strength and degradation resistance in addition to low halogen content can be advantageous as low halogen content polymeric materials are becoming increasingly desired due to environmental concerns. In one embodiment, the polyarylene sulfide composition can have a halogen content of less than about 1000 ppm, less than about 900 ppm, less than about 600 ppm, or less than about 400 ppm as determined according to an elemental analysis using Parr Bomb combustion followed by Ion Chromatography.

The disulfide compound can generally have the structure of:

R¹—S—S—R²

wherein R¹ and R² may be the same or different and are hydrocarbon groups that independently include from 1 to about 20 carbons. For instance, R¹ and R² may be an alkyl, cycloalkyl, aryl, or heterocyclic group. R¹ and R¹ may include reactive functionality at terminal end(s) of the disulfide compound. For example, at least one of R¹ and R² may include a terminal carboxyl group, hydroxyl group, a substituted or non-substituted amino group, a nitro group, or the like. In general, the reactive functionality can be selected such that the reactively functionalized polyarylene sulfide can react with the impact modifier. For example, when considering an epoxy-terminated impact modifier, the disulfide compound can include carboxyl and/or amine functionality.

Examples of disulfide compounds including reactive terminal groups as may be encompassed herein may include, without limitation, 2,2′-diaminodiphenyl disulfide, 3,3′-diaminodiphenyl disulfide, 4,4′-diaminodiphenyl disulfide, dibenzyl disulfide, dithiosalicyclic acid, dithioglycolic acid, α,α′-dithiodilactic acid, β,β′-dithiodilactic acid, 3,3′-dithiodipyridine, 4,4′dithiomorpholine, 2,2′-dithiobis(benzothiazole), 2,2′-dithiobis(benzimidazole), 2,2′-dithiobis(benzoxazole) and 2-(4′-morpholinodithio)benzothiazole.

The ratio of the amount of the polyarylene sulfide to the amount of the disulfide compound can be from about 1000:1 to about 10:1, from about 500:1 to about 20:1, or from about 400:1 to about 30:1.

In addition to the polyarylene sulfide polymer, the composition also includes an impact modifier. More specifically, the impact modifier can be an olefinic copolymer or terpolymer. For instance, the impact modifier can include ethylenically unsaturated monomer units have from about 4 to about 10 carbon atoms.

The impact modifier can be modified to include functionalization so as to react with the crosslinking agent. For instance, the impact modifier can be modified with a mole fraction of from about 0.01 to about 0.5 of one or more of the following: an α, β unsaturated dicarboxylic acid or salt thereof having from about 3 to about 8 carbon atoms; an α, β unsaturated carboxylic acid or salt thereof having from about 3 to about 8 carbon atoms; an anhydride or salt thereof having from about 3 to about 8 carbon atoms; a monoester or salt thereof having from about 3 to about 8 carbon atoms; a sulfonic acid or a salt thereof; an unsaturated epoxy compound having from about 4 to about 11 carbon atoms. Examples of such modification functionalities include maleic anhydride, fumaric acid, maleic acid, methacrylic acid, acrylic acid, and glycidyl methacrylate. Examples of metallic acid salts include the alkaline metal and transitional metal salts such as sodium, zinc, and aluminum salts.

A non-limiting listing of impact modifiers that may be used include ethylene-acrylic acid copolymer, ethylene-maleic anhydride copolymers, ethylene-alkyl(meth)acrylate-maleic anhydride terpolymers, ethylene-alkyl(meth)acrylate-glycidyl(meth)acrylate terpolymers, ethylene-acrylic ester-methacrylic acid terpolymer, ethylene-acrylic ester-maleic anhydride terpolymer, ethylene-methacrylic acid-methacrylic acid alkaline metal salt (ionomer) terpolymers, and the like. In one embodiment, for instance, an impact modifier can include a random terpolymer of ethylene, methylacrylate, and glycidyl methacrylate. The terpolymer can have a glycidyl methacrylate content of from about 5% to about 20%, such as from about 6% to about 10%. The terpolymer may have a methylacrylate content of from about 20% to about 30%, such as about 24%.

According to one embodiment, the impact modifier may be a linear or branched, homopolymer or copolymer (e.g., random, graft, block, etc.) containing epoxy functionalization, e.g., terminal epoxy groups, skeletal oxirane units, and/or pendent epoxy groups. For instance, the impact modifier may be a copolymer including at least one monomer component that includes epoxy functionalization. The monomer units of the impact modifier may vary. In one embodiment, for example, the impact modifier can include epoxy-functional methacrylic monomer units. As used herein, the term methacrylic generally refers to both acrylic and methacrylic monomers, as well as salts and esters thereof, e.g., acrylate and methacrylate monomers. Epoxy-functional methacrylic monomers as may be incorporated in the impact modifier may include, but are not limited to, those containing 1,2-epoxy groups, such as glycidyl acrylate and glycidyl methacrylate. Other suitable epoxy-functional monomers include allyl glycidyl ether, glycidyl ethacrylate, and glycidyl itoconate.

Other monomer units may additionally or alternatively be a component of the impact modifier. Examples of other monomers may include, for example, ester monomers, olefin monomers, amide monomers, etc. In one embodiment, the impact modifier can include at least one linear or branched—olefin monomer, such as those having from 2 to 20 carbon atoms, or from 2 to 8 carbon atoms. Specific examples include ethylene; propylene; 1-butene; 3-methyl-1-butene; 3,3-dimethyl-1-butene; 1-pentene; 1-pentene with one or more methyl, ethyl or propyl substituents; 1-hexene with one or more methyl, ethyl or propyl substituents; 1-heptene with one or more methyl, ethyl or propyl substituents; 1-octene with one or more methyl, ethyl or propyl substituents; 1-nonene with one or more methyl, ethyl or propyl substituents; ethyl, methyl or dimethyl-substituted 1-decene; 1-dodecene; and styrene.

Monomers included in an impact modifier that includes epoxy functionalization can include monomers that do not include epoxy functionalization, as long as at least a portion of the monomer units of the polymer are epoxy functionalized.

In one embodiment, the impact modifier can be a terpolymer that includes epoxy functionalization. For instance, the impact modifier can include a methacrylic component that includes epoxy functionalization, an α-olefin component, and a methacrylic component that does not include epoxy functionalization. For example, the impact modifier may be poly(ethylene-co-methylacrylate-co-glycidyl methacrylate), which has the following structure:

wherein, a, b, and c are 1 or greater.

In another embodiment the impact modifier can be a random copolymer of ethylene, ethyl acrylate and maleic anhydride having the following structure:

wherein x, y and z are 1 or greater.

The relative proportion of the various monomer components of a copolymeric impact modifier is not particularly limited. For instance, in one embodiment, the epoxy-functional methacrylic monomer components can form from about 1 wt. % to about 25 wt. %, or from about 2 wt. % to about 20 wt % of a copolymeric impact modifier. An a-olefin monomer can form from about 55 wt. % to about 95 wt. %, or from about 60 wt. % to about 90 wt. %, of a copolymeric impact modifier. When employed, other monomeric components (e.g., a non-epoxy functional methacrylic monomers) may constitute from about 5 wt. % to about 35 wt. %, or from about 8 wt. % to about 30 wt. %, of a copolymeric impact modifier.

An impact modifier may be formed according to standard polymerization methods as are generally known in the art. For example, a monomer containing polar functional groups may be grafted onto a polymer backbone to form a graft copolymer. Alternatively, a monomer containing functional groups may be copolymerized with a monomer to form a block or random copolymer using known free radical polymerization techniques, such as high pressure reactions, Ziegler-Natta catalyst reaction systems, single site catalyst (e.g., metallocene) reaction systems, etc.

Alternatively, an impact modifier may be obtained on the retail market. By way of example, suitable compounds for use as an impact modifier may be obtained from Arkema under the name Lotader®.

The molecular weight of the impact modifier can vary widely. For example, the impact modifier can have a number average molecular weight from about 7,500 to about 250,000 grams per mole, in some embodiments from about 15,000 to about 150,000 grams per mole, and in some embodiments, from about 20,000 to 100,000 grams per mole, with a polydispersity index typically ranging from 2.5 to 7.

In general, the impact modifier may be present in the composition in an amount from about 0.05% to about 40% by weight, from about 0.05% to about 37% by weight, or from about 0.1% to about 35% by weight.

Referring again to FIG. 6, the impact modifier can be added to the composition in conjunction with the polyarylene sulfide composition at the main feed throat 714 of the melt processing unit. This is not a requirement of the composition formation process, however, and in other embodiments, the impact modifier can be added downstream of the main feed throat. For instance, the impact modifier may be added at a location downstream from the point at which the polyarylene sulfide is supplied to the melt processing unit, but yet prior to the melting section, i.e., that length of the melt processing unit in which the polyarylene sulfide becomes molten. In another embodiment, the impact modifier may be added at a location downstream from the point at which the polyarylene sulfide becomes molten.

If desired, one or more distributive and/or dispersive mixing elements may be employed within the mixing section of the melt processing unit. Suitable distributive mixers for single screw extruders may include but are not limited to, for instance, Saxon, Dulmage, Cavity Transfer mixers, etc. Likewise, suitable dispersive mixers may include but are not limited to Blister ring, Leroy/Maddock, CRD mixers, etc. As is well known in the art, the mixing may be further improved by using pins in the barrel that create a folding and reorientation of the polymer melt, such as those used in Buss Kneader extruders, Cavity Transfer mixers, and Vortex Intermeshing Pin mixers.

In addition to the polyarylene sulfide and the impact modifier, the polyarylene composition can include a crosslinking agent. The crosslinking agent can be a polyfunctional compound or combination thereof that can react with functionality of the impact modifier to form crosslinks within and among the polymer chains of the impact modifier. In general, the crosslinking agent can be a non-polymeric compound, i.e., a molecular compound that includes two or more reactively functional terminal moieties linked by a bond or a non-polymeric (non-repeating) linking component. By way of example, the crosslinking agent can include but is not limited to di-epoxides, poly-functional epoxides, diisocyanates, polyisocyanates, polyhydric alcohols, water-soluble carbodiimides, diamines, diaminoalkanes, polyfunctional carboxylic acids, diacid halides, and so forth. For instance, when considering an epoxy-functional impact modifier, a non-polymeric polyfunctional carboxylic acid or amine can be utilized as a crosslinking agent.

Specific examples of polyfunctional carboxylic acid crosslinking agents can include, without limitation, isophthalic acid, terephthalic acid, phthalic acid, 1,2-di(p-carboxyphenyl)ethane, 4,4′-dicarboxydiphenyl ether, 4,4′-bisbenzoic acid, 1,4- or 1,5-naphthalene dicarboxylic acids, decahydronaphthalene dicarboxylic acids, norbornene dicarboxylic acids, bicyclooctane dicarboxylic acids, 1,4-cyclohexanedicarboxylic acid (both cis and trans), 1,4-hexylenedicarboxylic acid, adipic acid, azelaic acid, dicarboxyl dodecanoic acid, succinic acid, maleic acid, glutaric acid, suberic acid, azelaic acid and sebacic acid. The corresponding dicarboxylic acid derivatives, such as carboxylic acid diesters having from 1 to 4 carbon atoms in the alcohol radical, carboxylic acid anhydrides or carboxylic acid halides may also be utilized.

Exemplary diols useful as crosslinking agents can include, without limitation, aliphatic diols such as ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 2,2-dimethyl-1,3-propane diol, 2-ethyl-2-methyl-1,3-propane diol, 1,4-butane diol, 1,4-but-2-ene diol, 1,3-1,5-pentane diol, 1,5-pentane diol, dipropylene glycol, 2-methyl-1,5-pentane diol, and the like. Aromatic diols can also be utilized such as, without limitation, hydroquinone, catechol, resorcinol, methylhydroquinone, chlorohydroquinone, bisphenol A, tetrachlorobisphenol A, phenolphthalein, and the like. Exemplary cycloaliphatic diols as may be used include a cycloaliphatic moiety, for example 1,6-hexane diol, dimethanol decalin, dimethanol bicyclooctane, 1,4-cyclohexane dimethanol (including its cis- and trans-isomers), triethylene glycol, 1,10-decanediol, and the like.

Exemplary diamines that may be utilized as crosslinking agents can include, without limitation, isophorone-diamine, ethylenediamine, 1,2-, 1,3-propylene-diamine, N-methyl-1,3-propylene-diamine, N,N′-dimethyl-ethylene-diamine, and aromatic diamines, such as, for example, 2,4- and 2,6-toluoylene-diamine, 3,5-diethyl-2,4- and/or -2,6-toluoylene-diamine, and primary ortho-di-, tri- and/or tetra-alkyl-substituted 4,4′-diaminodiphenyl-methanes, (cyclo)aliphatic diamines, such as, for example, isophorone-diamine, ethylenediamine, 1,2-, 1,3-propylene-diamine, N-methyl-1,3-propylene-diamine, N,N′-dimethyl-ethylene-diamine, and aromatic diamines, such as, for example, 2,4- and 2,6-toluoylene-diamine, 3,5-diethyl-2,4- and/or -2,6-toluoylene-diamine, and primary ortho-di-, tri- and/or tetra-alkyl-substituted 4,4′-diaminodiphenyl-methanes.

In one embodiment, the composition can include a disulfide-free crosslinking agent. For example, the crosslinking agent can include carboxyl and/or amine functionality with no disulfide group that may react with the polyarylene sulfide. A crosslinking agent that is disulfide-free can be utilized so as to avoid excessive chain scission of the polyarylene sulfide by the crosslinking agent during formation of the composition. It should be understood, however, that the utilization of a disulfide-free crosslinking agent does not in any way limit the utilization of a reactively functionalized disulfide compound for functionalizing the polyarylene sulfide. For instance, in one embodiment, the composition can be formed according to a process that includes addition of a reactively functionalized disulfide compound to the melt processing unit that can reactively functionalize the polyarylene sulfide. The crosslinking agent utilized in this embodiment can then be a disulfide-free crosslinking agent that can include functionality that is reactive with the impact modifier as well as with the reactively functionalized polyarylene sulfide. Thus, the composition can be highly crosslinked without excessive scission of the polyarylene sulfide polymer chains.

In another embodiment the crosslinking agent and the polyarylene sulfide functionalization compound (when present) can be selected so as to encourage chain scission of the polyarylene sulfide. This may be beneficial, for instance, which chain scission is desired to decrease the melt viscosity of the polyarylene sulfide polymer.

The polyarylene sulfide composition may generally include the crosslinking agent in an amount from about 0.05 wt. % to about 2 wt. % by weight of the polyarylene sulfide composition, from about 0.07 wt. % to about 1.5 wt. % by weight of the polyarylene sulfide composition, or from about 0.1 wt. % to about 1.3 wt. %.

The crosslinking agent can be added to the melt processing unit following mixing of the polyarylene sulfide and the impact modifier. For instance, as illustrated in FIG. 6, the crosslinking agent can be added to the composition at a downstream location 716 following addition of polyarylene sulfide and the impact modifier (either together or separately) to the melt processing unit. This can ensure that the impact modifier has become dispersed throughout the polyarylene sulfide prior to addition of the crosslinking agent.

To help encourage distribution of the impact modifier throughout the melt prior to addition of the crosslinking agent, a variety of different parameters may be selectively controlled. For example, the ratio of the length (“L”) to diameter (“D”) of a screw of the melt processing unit may be selected to achieve an optimum balance between throughput and impact modifier distribution. For example, the L/D value after the point at which the impact modifier is supplied may be controlled to encourage distribution of the impact modifier. More particularly, the screw has a blending length (“L_(B)”) that is defined from the point at which both the impact modifier and the polyarylene sulfide are supplied to the unit (i.e., either where they are both supplied in conjunction with one another or the point at which the latter of the two is supplied) to the point at which the crosslinking agent is supplied, the blending length generally being less than the total length of the screw. For example, when considering a melt processing unit that has an overall L/D of 40, the L_(B)/D ratio of the screw can be from about 1 to about 36, in some embodiments from about 4 to about 20, and in some embodiments, from about 5 to about 15. In one embodiment, the L/L_(B) ratio can be from about 40 to about 1.1, from about 20 to about 2, or from about 10 to about 5.

Following addition of the crosslinking agent, the composition can be mixed to distribute the crosslinking agent throughout the composition and encourage reaction between the crosslinking agent, the impact modifier, and, in one embodiment, with the polyarylene sulfide.

The composition used to form the CFRT material can also include one or more additives as are generally known in the art. For example, one or more fillers can be included in the composition. One or more fillers may generally be included in the composition an amount of from about 5 wt. % to about 70 wt. %, or from about 20 wt. % to about 65 wt. % by weight of the CFRT composition.

The filler can be added to the composition according to standard practice. For instance, the filler can be added to the composition prior to or during combination of the composition with continuous fibers.

In one embodiment, non-continuous fibers can be included in the composition in conjunction with the continuous fibers. The fibers may include one or more fiber types including, without limitation, polymer fibers, glass fibers, carbon fibers, metal fibers, basalt fibers, and so forth, or a combination of fiber types. Non-continuous fiber sizes can vary as is known in the art. In one embodiment, the fibers can have an initial length of from about 3 mm to about 5 mm. Fiber diameters can vary depending upon the particular fiber used. The fibers, for instance, can have a diameter of less than about 100 μm, such as less than about 50 μm. For instance, non-continuous or continuous fibers can have a fiber diameter of from about 5 μm to about 50 μm, such as from about 5 μm to about 15 μm. The fibers may be pretreated with a sizing as is generally known.

Other fillers can be utilized. For instance, a particulate filler can be incorporated in the CFRT composition. In general, particulate fillers can encompass any particulate material having a median particle size of less than about 750 μm, for instance less than about 500 μm, or less than about 100 μm. In one embodiment, a particulate filler can have a median particle size in the range of from about 3 μm to about 20 μm. In addition, a particulate filler can be solid or hollow, as is known. Particulate fillers can also include a surface treatment, as is known in the art.

Particulate fillers can encompass one or more mineral fillers. For instance, the CFRT composition can include one or more mineral fillers in an amount of from about 1 wt. % to about 60 wt. % of the composition. Mineral fillers may include, without limitation, silica, quartz powder, silicates such as calcium silicate, aluminum silicate, kaolin, talc, mica, clay, diatomaceous earth, wollastonite, calcium carbonate, and so forth.

When incorporating multiple fillers, for instance a particulate filler and a non-continuous fiber filler, the fillers may be added together or separately to the melt processing unit. For instance, a particulate filler can be added to the main feed with the thermoplastic polymer or downstream prior to addition of a fibrous filler, and a fibrous filler can be added further downstream of the addition point of the particulate filler. In general, a non-continuous fibrous filler can be added downstream of any other fillers such as a particulate filler, though this is not a requirement.

A filler can be an electrically conductive filler such as, without limitation, carbon black, graphite, graphene, carbon fiber, carbon nanotubes, a metal powder, and so forth. In those embodiments in which the composition includes electrically conductive fillers, adequate electrically conductive filler can be included such that the composition has a volume specific resistance of equal to or less than about 10⁹ ohms cm.

In one embodiment, the CFRT composition can include a UV stabilizer as an additive. For instance, the CFRT composition can include a UV stabilizer in an amount of between about 0.5 wt. % and about 15 wt. %, between about 1 wt. % and about 8 wt. %, or between about 1.5 wt. % and about 7 wt. % of a UV stabilizer. One particularly suitable UV stabilizer that may be employed is a hindered amine UV stabilizer. Suitable hindered amine UV stabilizer compounds may be derived from a substituted piperidine, such as alkyl-substituted piperidyl, piperidinyl, piperazinone, alkoxypiperidinyl compounds, and so forth. For example, the hindered amine may be derived from a 2,2,6,6-tetraalkylpiperidinyl. The hindered amine may, for example, be an oligomeric or polymeric compound having a number average molecular weight of about 1,000 or more, in some embodiments from about 1000 to about 20,000, in some embodiments from about 1500 to about 15,000, and in some embodiments, from about 2000 to about 5000. Such compounds typically contain at least one 2,2,6,6-tetraalkylpiperidinyl group (e.g., 1 to 4) per polymer repeating unit. One particularly suitable high molecular weight hindered amine is commercially available from Clariant under the designation Hostavin® N30 (number average molecular weight of 1200). Another suitable high molecular weight hindered amine is commercially available from Adeka Palmarole SAS under the designation ADK STAB® LA-63 and ADK STAB® LA-68.

In addition to the high molecular hindered amines, low molecular weight hindered amines may also be employed. Such hindered amines are generally monomeric in nature and have a molecular weight of about 1000 or less, in some embodiments from about 155 to about 800, and in some embodiments, from about 300 to about 800.

Other suitable UV stabilizers may include UV absorbers, such as benzotriazoles or benzopheones, which can absorb UV radiation.

An additive that may be included in a CFRT composition is one or more colorants as are generally known in the art. For instance, the composition can include from about 0.1 wt. % to about 10 wt. %, or from about 0.2 wt. % to about 5 wt. % of one or more colorants. As utilized herein, the term “colorant” generally refers to any substance that can impart color to a material. Thus, the term “colorant” encompasses both dyes, which exhibit solubility in an aqueous solution, and pigments, that exhibit little or no solubility in an aqueous solution.

Other additives that can be included in the CFRT composition can encompass, without limitation, antimicrobials, lubricants, impact modifiers such as those discussed above with regard to a polyarylene sulfide composition, antioxidants, stabilizers (e.g., heat stabilizers including organophosphites such as Doverphos® products available from Dover Chemical Corporation), surfactants, flow promoters, solid solvents, and other materials added to enhance properties and processability. Such optional materials may be employed in the CFRT composition in conventional amounts and according to conventional processing techniques, for instance through addition to the composition at the main feed throat of a melt processing unit.

Following addition of all components to the composition, the composition can thoroughly mixed in and combined with the continuous fiber reinforcement. The final extrudate can be in the form of a pultruded tape or ribbon.

In some embodiments, as shown in FIG. 4, a barrier layer 120 according to the present disclosure is a tape, such as a tape 152 or tape 156 as discussed below, formed from the CFRT material. The tape may be wrapped around hollow body 102 to surround the hollow body 102. For example, in some exemplary embodiments as shown in FIG. 4, the tape may be wrapped around the hollow body 102 generally helically with respect to the longitudinal axis 110 of the hollow body 102.

A tape according to the present disclosure may be formed using any suitable process or apparatus. Exemplary embodiments of suitable processes and apparatus, such as pultrusion processes and apparatus, for forming a tape that may be a barrier layer 120 according to the present disclosure are discussed in detail below.

Referring to FIG. 7, one embodiment of such an extrusion device is shown. More particularly, the apparatus includes an extruder 130 containing a screw shaft 134 mounted inside a barrel 132. A heater 136 (e.g., electrical resistance heater) is mounted outside the barrel 132. During use, a feedstock 137 is supplied to the extruder 130 through a hopper 138. The feedstock is formed from a thermoplastic material as discussed above. The feedstock 137 is conveyed inside the barrel 132 by the screw shaft 134 and heated by frictional forces inside the barrel 132 and by the heater 136. Upon being heated, the feedstock 137 exits the barrel 132 through a barrel flange 138 and enters a die flange 139 of an impregnation die 150.

A continuous fiber roving 142 or a plurality of continuous fiber rovings 142 are supplied from a reel or reels 144 to die 150. The rovings 142 are generally positioned side-by-side, with minimal to no distance between neighboring rovings, before impregnation. The feedstock 137 may further be heated inside the die by heaters 146 mounted in or around the die 150. The die is generally operated at temperatures that are sufficient to cause and/or maintain the proper melt temperature for the thermoplastic material, thus allowing for the desired level of impregnation of the rovings by the thermoplastic material. Typically, the operation temperature of the die is higher than the melt temperature of the thermoplastic material, such as at temperatures from about 200° C. to about 450° C. When processed in this manner, the continuous fiber rovings 142 become embedded in the thermoplastic material, which may be a resin 214 processed from the feedstock 137. The mixture may then exit the impregnation die 150 as wetted composite, extrudate, or tape 152.

As used herein, the term “roving” generally refers to a bundle of individual fibers 300. The fibers 300 contained within the roving can be twisted or can be straight. The rovings may contain a single fiber type or different types of fibers 300. Different fibers may also be contained in individual rovings or, alternatively, each roving may contain a different fiber type. The continuous fibers employed in the rovings possess a high degree of tensile strength relative to their mass. For example, the ultimate tensile strength of the fibers is typically from about 1,000 to about 15,000 Megapascals (“MPa”), in some embodiments from about 2,000 MPa to about 10,000 MPa, and in some embodiments, from about 3,000 MPa to about 6,000 MPa. Such tensile strengths may be achieved even though the fibers are of a relatively light weight, such as a mass per unit length of from about 0.05 to about 2 grams per meter, in some embodiments from about 0.4 to about 1.5 grams per meter. The ratio of tensile strength to mass per unit length may thus be about 1,000 Megapascals per gram per meter (“MPa/g/m”) or greater, in some embodiments about 4,000 MPa/g/m or greater, and in some embodiments, from about 5,500 to about 20,000 MPa/g/m. Carbon fibers are particularly suitable for use as the continuous fibers, which typically have a tensile strength to mass ratio in the range of from about 5,000 to about 7,000 MPa/g/m. The continuous fibers often have a nominal diameter of about 4 to about 35 micrometers, and in some embodiments, from about 9 to about 35 micrometers. The number of fibers contained in each roving can be constant or vary from roving to roving. Typically, a roving contains from about 1,000 fibers to about 50,000 individual fibers, and in some embodiments, from about 5,000 to about 30,000 fibers.

A pressure sensor 147 may sense the pressure near the impregnation die 150 to allow control to be exerted over the rate of extrusion by controlling the rotational speed of the screw shaft 134, or the feed rate of the feeder. That is, the pressure sensor 147 is positioned near the impregnation die 150, such as upstream of the manifold assembly 220, so that the extruder 130 can be operated to deliver a correct amount of resin 214 for interaction with the fiber rovings 142. After leaving the impregnation die 150, impregnated rovings 142 or the extrudate or tape 152, which may comprises the CFRT material, may enter an optional pre-shaping or guiding section (not shown) and/or a preheating device to control the temperature of the extrudate before entering a nip formed between two adjacent rollers 190. Although optional, the rollers 190 can help to consolidate the impregnated rovings 142 into a tape 156 or consolidate the tape 152 into a final tape 156, as well as enhance fiber impregnation and squeeze out any excess voids. In addition to the rollers 190, other shaping devices may also be employed, such as a die system. Regardless, the resulting consolidated tape 156 is pulled by tracks 162 and 164 mounted on rollers. The tracks 162 and 164 also pull the impregnated rovings 142 or tape 152 from the impregnation die 150 and through the rollers 190. If desired, the consolidated tape 156 may be wound up at a section 171. Generally speaking, the resulting tapes are relatively thin and typically have a thickness of from about 0.05 to about 1 millimeter, in some embodiments from about 0.1 to about 0.8 millimeters, and in some embodiments, from about 0.1 to about 0.4 millimeters.

Perspective views of one embodiment of a die 150 according to the present disclosure are further shown in FIGS. 7 and 8. As shown, resin 214 is flowed into the die 150 as indicated by resin flow direction 244. The resin 214 is distributed within the die 150 and then interacted with the rovings 142. The rovings 142 are traversed through the die 150 in roving run direction 282, and are coated with resin 214. The rovings 142 are then impregnated with the resin 214, and these impregnated rovings 142 exit the die 150. In some embodiments, as shown in FIG. 7, the impregnated rovings 142 are connected by the resin 214 and thus exist as tape 152. In other embodiments, as shown in FIGS. 8 and 9, the impregnated rovings 142 exit the die separately, each impregnated within resin 214.

Within the impregnation die, it is generally desired that the rovings 142 are traversed through an impregnation zone 250 to impregnate the rovings with the polymer resin 214. In the impregnation zone 250, the polymer resin may be forced generally transversely through the rovings by shear and pressure created in the impregnation zone 250, which significantly enhances the degree of impregnation. This is particularly useful when forming a composite from tapes of a high fiber content, such as about 35% weight fraction (“Wf”) or more, and in some embodiments, from about 40% Wf or more. Typically, the die 150 will include a plurality of contact surfaces 252, such as for example at least 2, at least 3, from 4 to 7, from 2 to 20, from 2 to 30, from 2 to 40, from 2 to 50, or more contact surfaces 252, to create a sufficient degree of penetration and pressure on the rovings 142. Although their particular form may vary, the contact surfaces 252 typically possess a curvilinear surface, such as a curved lobe, pin, etc. The contact surfaces 252 are also typically made of a metal material.

FIG. 9 shows a cross-sectional view of an impregnation die 150. As shown, the impregnation die 150 includes a manifold assembly 220 and an impregnation section. The impregnation section includes an impregnation zone 250. In some embodiments, the impregnation section additionally includes a gate passage 270. The manifold assembly 220 is provided for flowing the polymer resin 214 therethrough. For example, the manifold assembly 220 may include a channel 222 or a plurality of channels 222. The resin 214 provided to the impregnation die 150 may flow through the channels 222.

As shown in FIG. 10, in exemplary embodiments, at least a portion of each of the channels 222 may be curvilinear. The curvilinear portions may allow for relatively smooth redirection of the resin 214 in various directions to distribute the resin 214 through the manifold assembly 220, and may allow for relatively smooth flow of the resin 214 through the channels 222. Alternatively, the channels 222 may be linear, and redirection of the resin 214 may be through relatively sharp transition areas between linear portions of the channels 222. It should further be understood that the channels 222 may have any suitable shape, size, and/or contour.

The plurality of channels 222 may, in exemplary embodiments as shown in FIG. 10, be a plurality of branched runners 222. The runners 222 may include a first branched runner group 232. The first branched runner group 232 includes a plurality of runners 222 branching off from an initial channel or channels 222 that provide the resin 214 to the manifold assembly 220. The first branched runner group 232 may include 2, 3, 4 or more runners 222 branching off from the initial channels 222.

If desired, the runners 222 may include a second branched runner group 234 diverging from the first branched runner group 232, as shown. For example, a plurality of runners 222 from the second branched runner group 234 may branch off from one or more of the runners 222 in the first branched runner group 232. The second branched runner group 234 may include 2, 3, 4 or more runners 222 branching off from runners 222 in the first branched runner group 232.

If desired, the runners 222 may include a third branched runner group 236 diverging from the second branched runner group 234, as shown. For example, a plurality of runners 222 from the third branched runner group 236 may branch off from one or more of the runners 222 in the second branched runner group 234. The third branched runner group 236 may include 2, 3, 4 or more runners 222 branching off from runners 222 in the second branched runner group 234.

In some exemplary embodiments, as shown, the plurality of branched runners 222 have a symmetrical orientation along a central axis 224. The branched runners 222 and the symmetrical orientation thereof generally evenly distribute the resin 214, such that the flow of resin 214 exiting the manifold assembly 220 and coating the rovings 142 is substantially uniformly distributed on the rovings 142. This desirably allows for generally uniform impregnation of the rovings 142.

Further, the manifold assembly 220 may in some embodiments define an outlet region 242. The outlet region 242 is that portion of the manifold assembly 220 wherein resin 214 exits the manifold assembly 220. Thus, the outlet region 242 generally encompasses at least a downstream portion of the channels or runners 222 from which the resin 214 exits. In some embodiments, as shown, at least a portion of the channels or runners 222 disposed in the outlet region 242 have an increasing area in a flow direction 244 of the resin 214. The increasing area allows for diffusion and further distribution of the resin 214 as the resin 214 flows through the manifold assembly 220, which further allows for substantially uniform distribution of the resin 214 on the rovings 142. Additionally or alternatively, various channels or runners 222 disposed in the outlet region 242 may have constant areas in the flow direction 244 of the resin 214, or may have decreasing areas in the flow direction 244 of the resin 214.

In some embodiments, as shown, each of the channels or runners 222 disposed in the outlet region 242 is positioned such that resin 214 flowing therefrom is combined with resin 214 from other channels or runners 222 disposed in the outlet region 242. This combination of the resin 214 from the various channels or runners 222 disposed in the outlet region 242 produces a generally singular and uniformly distributed flow of resin 214 from the manifold assembly 220 to substantially uniformly coat the rovings 142. Alternatively, various of the channels or runners 222 disposed in the outlet region 242 may be positioned such that resin 214 flowing therefrom is discrete from the resin 214 from other channels or runners 222 disposed in the outlet region 242. In these embodiments, a plurality of discrete but generally evenly distributed resin flows 214 may be produced by the manifold assembly 220 for substantially uniformly coating the rovings 142.

As shown in FIG. 9, at least a portion of the channels or runners 222 disposed in the outlet region 242 have curvilinear cross-sectional profiles. These curvilinear profiles allow for the resin 214 to be gradually directed from the channels or runners 222 generally downward towards the rovings 142. Alternatively, however, these channels or runners 222 may have any suitable cross-sectional profiles.

As further illustrated in FIGS. 9 and 10, after flowing through the manifold assembly 220, the resin 214 may flow through gate passage 270. Gate passage 270 is positioned between the manifold assembly 220 and the impregnation zone 250, and is provided for flowing the resin 214 from the manifold assembly 220 such that the resin 214 coats the rovings 142. Thus, resin 214 exiting the manifold assembly 220, such as through outlet region 242, may enter gate passage 270 and flow therethrough.

In some embodiments, as shown in FIG. 9, the gate passage 270 extends vertically between the manifold assembly 220 and the impregnation zone 250. Alternatively, however, the gate passage 270 may extend at any suitable angle between vertical and horizontal such that resin 214 is allowed to flow therethrough.

Further, as shown in FIG. 9, in some embodiments at least a portion of the gate passage 270 has a decreasing cross-sectional profile in the flow direction 244 of the resin 214. This taper of at least a portion of the gate passage 270 may increase the flow rate of the resin 214 flowing therethrough before it contacts the rovings 142, which may allow the resin 214 to impinge on the rovings 142. Initial impingement of the rovings 142 by the resin 214 provides for further impregnation of the rovings, as discussed below. Further, tapering of at least a portion of the gate passage 270 may increase backpressure in the gate passage 270 and the manifold assembly 220, which may further provide more even, uniform distribution of the resin 214 to coat the rovings 142. Alternatively, the gate passage 270 may have an increasing or generally constant cross-sectional profile, as desired or required.

Upon exiting the manifold assembly 220 and the gate passage 270 of the die 150 as shown in FIG. 9, the resin 214 contacts the rovings 142 being traversed through the die 150. As discussed above, the resin 214 may substantially uniformly coat the rovings 142, due to distribution of the resin 214 in the manifold assembly 220 and the gate passage 270. Further, in some embodiments, the resin 214 may impinge on an upper surface of each of the rovings 142, or on a lower surface of each of the rovings 142, or on both an upper and lower surface of each of the rovings 142. Initial impingement on the rovings 142 provides for further impregnation of the rovings 142 with the resin 214. Impingement on the rovings 142 may be facilitated by the velocity of the resin 214 when it impacts the rovings 142, the proximity of the rovings 142 to the resin 214 when the resin exits the manifold assembly 220 or gate passage 270, or other various variables.

As shown in FIG. 9, the coated rovings 142 are traversed in run direction 282 through impregnation zone 250. The impregnation zone 250 is in fluid communication with the manifold assembly 220, such as through the gate passage 270 disposed therebetween. The impregnation zone 250 is configured to impregnate the rovings 142 with the resin 214.

For example, as discussed above, in exemplary embodiments as shown in FIGS. 9 and 11 through 13, the impregnation zone 250 includes a plurality of contact surfaces 252. The rovings 142 are traversed over the contact surfaces 252 in the impregnation zone. Impingement of the rovings 142 on the contact surface 252 creates shear and pressure sufficient to impregnate the rovings 142 with the resin 214 coating the rovings 142.

In some embodiments, as shown in FIGS. 9, 12 and 13, the impregnation zone 250 is defined between two spaced apart opposing impregnation plates 256 and 258, which may be included in the impregnation section. First plate 256 defines a first inner surface 257, while second plate 258 defines a second inner surface 259. The impregnation zone 250 is defined between the first plate 256 and the second plate 258. The contact surfaces 252 may be defined on or extend from both the first and second inner surfaces 257 and 259, or only one of the first and second inner surfaces 257 and 259.

In exemplary embodiments, as shown in FIGS. 9, 12 and 13, the contact surfaces 252 may be defined alternately on the first and second surfaces 257 and 259 such that the rovings alternately impinge on contact surfaces 252 on the first and second surfaces 257 and 259. Thus, the rovings 142 may pass contact surfaces 252 in a waveform, tortuous or sinusoidual-type pathway, which enhances shear.

Angle 254 at which the rovings 142 traverse the contact surfaces 252 may be generally high enough to enhance shear and pressure, but not so high to cause excessive forces that will break the fibers. Thus, for example, the angle 254 may be in the range between approximately 1° and approximately 30°, and in some embodiments, between approximately 5° and approximately 25°.

As stated above, contact surfaces 252 typically possess a curvilinear surface, such as a curved lobe, pin, etc. In exemplary embodiments as shown, a plurality of peaks, which may form contact surfaces 252, and valleys are thus defined. Further, in many exemplary embodiments, the impregnation zone 250 has a waveform cross-sectional profile. In one exemplary embodiment as shown in FIGS. 9 and 11 through 13, the contact surfaces 252 are lobes that form portions of the waveform surfaces of both the first and second plates 256 and 258 and define the waveform cross-sectional profile. FIG. 11 illustrates the second plate 258 and the various contact surfaces thereon that form at least a portion of the impregnation zone 250 according to some of these embodiments.

In other embodiments, the contact surfaces 252 are lobes that form portions of a waveform surface of only one of the first or second plate 256 or 258. In these embodiments, impingement occurs only on the contact surfaces 252 on the surface of the one plate. The other plate may generally be flat or otherwise shaped such that no interaction with the coated rovings occurs.

In other alternative embodiments, the impregnation zone 250 may include a plurality of pins (or rods), each pin having a contact surface 252. The pins may be static, freely rotational (not shown), or rotationally driven. Further, the pins may be mounted directly to the surface of the plates defining the impingement zone, or may be spaced from the surface. It should be noted that the pins may be heated by heaters 143, or may be heated individually or otherwise as desired or required. Further, the pins may be contained within the die 150, or may extend outwardly from the die 150 and not be fully encased therein.

In further alternative embodiments, the contact surfaces 252 and impregnation zone 250 may comprise any suitable shapes and/or structures for impregnating the rovings 142 with the resin 214 as desired or required.

As discussed, a roving 142 traversed through an impregnation zone 250 according to the present disclosure may become impregnated by resin 214, thus resulting in an impregnated roving 142, and optionally a tape 152 comprising at least one roving 142, exiting the impregnation zone 250, such as downstream of the contact surfaces 252 in the run direction 282. The impregnated rovings 142 and optional tape 152 exiting the impregnation zone 250 are thus formed from a fiber impregnated polymer material, as discussed above. At least one fiber roving 142 may be contained within a thermoplastic material, or resin, 214, as discussed above, to form the CFRT material and resulting tape 152 or tape 156.

As further shown in FIGS. 8 and 9, in some embodiments, a faceplate 290 may adjoin or be adjacent to the impregnation zone 250. The faceplate 290 may be positioned downstream of the impregnation zone 250 and, if included, the land zone 280, in the run direction 282. The faceplate 290 may contact other components of the die 150, such as the impregnation zone 250 or land zone 280, or may be spaced therefrom. Faceplate 290 is generally configured to meter excess resin 214 from the rovings 142. Thus, apertures in the faceplate 290, through which the rovings 142 traverse, may be sized such that when the rovings 142 are traversed therethrough, the size of the apertures causes excess resin 214 to be removed from the rovings 142.

As shown in FIG. 7, in alternative embodiments, the die 150 may lack a faceplate 290. Further, in some embodiments, the formation and maintenance of a tape 152 within and exited from a die 150 of the present disclosure may be facilitated through the lack of or removal of a faceplate from the die 150. Removal of the faceplate 290 allows for a plurality of rovings 142 exiting a die 150 to exit as a single sheet or tape 152, rather than as separated rovings 142 due to metering through the faceplate. This could potentially eliminate the need to later form these rovings 142 into such a sheet or tape 156. Removal of the faceplate 290 may have additional advantages. For example, removal may prevent clogging of the faceplate with resin 214, which can disrupt the traversal of rovings 142 therethrough. Additionally, removal may allow for easier access to the impregnation zone 250, and may thus make it easier to introduce and reintroduce rovings 142 to the impregnation zone 250 during start-up, after temporary disruptions such as due to breakage of a roving 142, or during any other suitable time period.

It should be understood that a tape 152, 156 according to the present disclosure may have any suitable cross-sectional shape and/or size. For example, such tape 152, 156 may have a generally rectangular shape, or a generally oval or circular or other suitable polygonal or otherwise shape. Further, it should be understood that one or more impregnated rovings 142 having been traversed through the impregnation zone 250 may together form the tape 152, 156, with the resin 214 of the various rovings 142 connected to form such tape 152, 156. The various above amounts, ranges, and/or ratios may thus in exemplary embodiments be determined for a tape 152 having any suitable number of impregnated rovings 142 embedded and generally dispersed within resin 214.

To further facilitate impregnation of the rovings 142, they may also be kept under tension while present within the die 150, and specifically within the impregnation zone 250. The tension may, for example, range from about 5 to about 300 Newtons, in some embodiments from about 50 to about 250 Newtons, and in some embodiments, from about 100 to about 200 Newtons per roving 142 or tow of fibers.

As shown in FIGS. 14 and 15, in some embodiments, a land zone 280 may be positioned downstream of the impregnation zone 250 in run direction 282 of the rovings 142. The rovings 142 may traverse through the land zone 280 before exiting the die 150. In some embodiments, as shown in FIG. 14, at least a portion of the land zone 280 may have an increasing cross-sectional profile in run direction 282, such that the area of the land zone 280 increases. The increasing portion may be the downstream portion of the land zone 280 to facilitate the rovings 142 exiting the die 150. Alternatively, the cross-sectional profile or any portion thereof may decrease, or may remain constant as shown in FIG. 15.

Additionally, other components may be optionally employed to assist in the impregnation of the fibers. For example, a “gas jet” assembly may be employed in certain embodiments to help uniformly spread a roving of individual fibers, which may each contain up to as many as 24,000 fibers, across the entire width of the merged tow. This helps achieve uniform distribution of strength properties. Such an assembly may include a supply of compressed air or another gas that impinges in a generally perpendicular fashion on the moving rovings that pass across exit ports. The spread rovings may then be introduced into a die for impregnation, such as described above.

It should be understood that tapes 152, 156 and impregnated rovings 142 thereof according to the present disclosure need not be formed in the dies 150 and other apparatus as discussed above. Such dies 150 and apparatus are merely disclosed as examples of suitable equipment for forming tapes 152, 156. The use of any suitable equipment or process to form tapes 152, 156 is within the scope and spirit of the present disclosure.

The tapes 152 that result from use of the die and method according to the present disclosure may have a very low void fraction, which helps enhance their strength. For instance, the void fraction may be about 3% or less, in some embodiments about 2% or less, in some embodiments about 1.5% or less, in some embodiments about 1% or less, and in some embodiments, about 0.5% or less. The void fraction may be measured using techniques well known to those skilled in the art. For example, the void fraction may be measured using a “resin burn off” test in which samples are placed in an oven (e.g., at 600° C. for 3 hours) to burn out the resin. The mass of the remaining fibers may then be measured to calculate the weight and volume fractions. Such “burn off” testing may be performed in accordance with ASTM D 2584-08 to determine the weights of the fibers and the polymer matrix, which may then be used to calculate the “void fraction” based on the following equations:

V _(f)=100*(ρ_(t)−ρ_(c))/ρ_(t)

where,

V_(f) is the void fraction as a percentage;

ρ_(c) is the density of the composite as measured using known techniques, such as with a liquid or gas pycnometer (e.g., helium pycnometer);

ρ_(t) is the theoretical density of the composite as is determined by the following equation:

ρ_(t)=1/[W _(f)/ρ_(f) +W _(m)/ρ_(m)]

ρ_(m) is the density of the polymer matrix (e.g., at the appropriate crystallinity);

ρ_(f) is the density of the fibers;

W_(f) is the weight fraction of the fibers; and

W_(m) is the weight fraction of the polymer matrix.

Alternatively, the void fraction may be determined by chemically dissolving the resin in accordance with ASTM D 3171-09. The “burn off” and “dissolution” methods are particularly suitable for glass fibers, which are generally resistant to melting and chemical dissolution. In other cases, however, the void fraction may be indirectly calculated based on the densities of the polymer, fibers, and tape in accordance with ASTM D 2734-09 (Method A), where the densities may be determined ASTM D792-08 Method A. Of course, the void fraction can also be estimated using conventional microscopy equipment.

As discussed above, after exiting an impregnation die 150, the impregnated rovings 142 may in some embodiments form a tape 152. The tape 152 may be consolidated into a consolidated tape 156. The number of rovings employed in each tape 152, 156 may vary. Typically, however, a tape 152, 156 will contain from 2 to 80 rovings, and in some embodiments from 10 to 60 rovings, and in some embodiments, from 20 to 50 rovings. In some embodiments, it may be desired that the rovings are spaced apart approximately the same distance from each other within the tape 152, 156. In other embodiments, however, it may be desired that the rovings are combined, such that the fibers of the rovings are generally evenly distributed throughout the tape 152, 156, such as throughout one or more resin rich portions and a fiber rich portion as discussed above. In these embodiments, the rovings may be generally indistinguishable from each other. Referring to FIGS. 16 and 17, for example, embodiments of a tape 152 are shown that contains rovings that are combined such that the fibers are generally evenly distributed within a fiber rich portion thereof. As shown in FIG. 16, in exemplary embodiments, the fibers extend generally unidirectionally along a longitudinal axis of the tape 152.

A relatively high percentage of fibers may be employed in a tape, and CFRT material thereof, to provide enhanced strength properties. For instance, fibers typically constitute from about 25 wt. % to about 90 wt. %, in some embodiments from about 30 wt. % to about 75 wt. %, and in some embodiments, from about 35 wt. % to about 70 wt. % of the tape or material thereof. Likewise, polymer(s) typically constitute from about 20 wt. % to about 75 wt. %, in some embodiments from about 25 wt. % to about 70 wt. %, and in some embodiments, from about 30 wt. % to about 65 wt. % of the tape 152, 156. Such percentage of fibers may additionally or alternatively by measured as a volume fraction. For example, in some embodiments, the CFRT material may have a fiber volume fraction between approximately 25% and approximately 80%, in some embodiments between approximately 30% and approximately 70%, in some embodiments between approximately 40% and approximately 60%, and in some embodiments between approximately 45% and approximately 55%.

Thus, as discussed, in exemplary embodiments, a barrier layer 120 according to the present disclosure may be formed from a CFRT material tape 152, 156. Referring again to FIG. 3, one embodiment of a pipe section 100 is illustrated. As shown, the pipe section 100 has several concentric layers. The innermost layer is the hollow body 102, formed from a metal material. The barrier layer 120 surrounds and is immediately adjacent the hollow body 102. The barrier layer 120 is formed of CFRT material and provides strength and flexibility while preventing permeation of the fluid carried by the hollow body 102 through the wall thereof. In addition, the barrier layer 120 can resist degradation by both the fluid carried by the hollow body 102 (e.g., the production fluid, the injection fluid, etc.) as well as by temperature conditions under which the pipe section 100 is utilized.

The pipe section 100 may also include a number of other various layers, each of which may be bonded to neighboring layers or left unbonded. For example, the pipe section 100 may also include an outer layer 822 that provides an external sleeve and an external fluid barrier as well as providing protection to the pipe section 100 from external damage due to, e.g., abrasion or encounters with environmental materials. The outer layer 822 can be formed of a polymeric material such as a polyarylene sulfide composition or a high density polyethylene that can resist both mechanical damage and intrusion of seawater to the inner layers of the pipe section 100. According to one embodiment, the outer layer 822 can be a composite material that includes a polymeric material in conjunction with a reinforcement material such as carbon fibers, carbon steel fibers, or glass fibers.

A hoop strength layer 804 can be located external to the barrier layer to increase the ability of the pipe section 100 to withstand hoop stresses caused by forced applied to the pipe section 100 wall by a pressure differential. The hoop strength layer can generally be a metal layer formed of, e.g., a helically wound strip of carbon steel that can form a layer of from about 3 to about 7 millimeters in thickness. The hoop strength layer can resist both internal pressure and bending of the pipe section 100. In one embodiment, the carbon steel strip that forms the hoop strength layer 804 can define an interlocking profile, for instance an S- or Z-cross-sectional configuration, such that adjacent windings interlock with one another to form a stronger layer. In one embodiment, the hoop strength layer can include multiple materials for added strength. For example, in an embodiment in which design and pressure requirements call for higher burst strengths, a second flat metal strip can be helically wound over the interlocked metal strips of the hoop strength layer to provide additional strength for this layer. An intervening polymeric layer such as an anti-wear layer discussed further herein can optionally be located between the two layers of the hoop strength layer as well.

Additional strength layers 818 and 820 can be formed of helically-wound metal (generally carbon steel) strips. The strength layers 818 and 820 can be separated from the hoop strength layer 804 and from each other by polymeric anti-wear layers 817 and 819. The strength layers 818 and 820 can provide additional hoop strength as well as axial strength to the pipe section 100. Though the pipe section 100 includes two strength layers 818, 820, it should be understood that a pipe section 100 may include any suitable number of strength layers, including no strength layers, one, two, three, or more strength layers. In general, the helically wound metal strips of strength layers 818 and 820 will overlap but need not interlock. As such, the strength layers 818, 820 may have a width of from about 1 millimeter to about 5 millimeters.

The intervening anti-wear layers 817, 819 can be formed of a polymer such as a polyarylene sulfide, a polyamide, a high density polyethylene, or the like. In one embodiment, the anti-wear layers 817, 819 can be a composite material that includes unidirectional fibers, for instance carbon or glass fibers. For instance, the anti-wear layers 817, 819 can be formed of a polymer tape or fiber-reinforced polymer tape such as a pultruded polymer tape or ribbon that is helically wound over each strength layer. The anti-wear layers 817, 819 can prevent wear of the adjacent strength layers that can come about due to motion of the strips forming the layers. The anti-wear layers 817, 819 can also prevent birdcaging of the adjacent layers. As with the strength layers 818, 820 of the pipe section 100, the number of anti-wear layers is not particularly limited, and a pipe section 100 can include no anti-wear layers, one anti-wear layers, or multiple anti-wear layers depending upon the depth and local environment in which the pipe section 100 will be utilized, the fluid to be carried by the hollow body 102, and so forth. The anti-wear layers 817, 819, can be relatively thin, for instance between about 0.2 and about 1.5 millimeters.

A pipe section 100 may include additional layers as are generally known in the art. For example, a pipe section 100 may include an insulation layer, for instance immediately internal to the outer layer 822. An insulation layer, when present can be formed of a foam, fibrous mat, or any other insulation material as is known. By way of example, single or multiple layers of an insulation tape can be wound onto the outer strength layer to form an insulation layer between the outer strength layer 820 and the outer layer 822.

It should be understood that the various layers surrounding the barrier layer 120 as shown in FIG. 3 may similarly be utilized in any suitable pipe sections 100, such as those shown in FIGS. 4 and 5.

Embodiments of the present disclosure are illustrated by the following examples that are merely for the purpose of illustration of embodiments and are not to be regarded as limiting the scope of the invention or the manner in which it may be practiced. Unless specifically indicated otherwise, parts and percentages are given by weight.

Formation and Test Methods

Injection Molding Process: Tensile bars are injection molded to ISO 527-1 specifications according to standard ISO conditions.

Melt Viscosity: All materials are dried for 1.5 hours at 150° C. under vacuum prior to testing. The melt viscosity is measured on a capillary rheometer at 316° C. and 400 sec⁻¹ with the viscosity measurement taken after five minutes of constant shear.

Tensile Properties: Tensile properties including tensile modulus, yield stress, yield strain, strength at break, elongation at yield, elongation at break, etc. are tested according to ISO Test No. 527 (technically equivalent to ASTM D638). Modulus, strain, and strength measurements are made on the same test strip sample having a length of 80 mm, thickness of 10 mm, and width of 4 mm. The testing temperature is 23° C., and the testing speeds are 5 or 50 mm/min.

Flexural Properties: Flexural properties including flexural strength and flexural modulus are tested according to ISO Test No. 178 (technically equivalent to ASTM D790). This test is performed on a 64 mm support span. Tests are run on the center portions of uncut ISO 3167 multi-purpose bars. The testing temperature is 23° C. and the testing speed is 2 mm/min.

Deflection Temperature Under Load (“DTUL”): The deflection under load temperature was determined in accordance with ISO Test No. 75-2 (technically equivalent to ASTM D648-07). More particularly, a test strip sample having a length of 80 mm, thickness of 10 mm, and width of 4 mm was subjected to an edgewise three-point bending test in which the specified load (maximum outer fibers stress) was 1.8 Megapascals. The specimen was lowered into a silicone oil bath where the temperature is raised at 2° C. per minute until it deflects 0.25 mm (0.32 mm for ISO Test No. 75-2).

Notched Charpy Impact Strength: Notched Charpy properties are tested according to ISO Test No. ISO 179-1) (technically equivalent to ASTM D256, Method B). This test is run using a Type A notch (0.25 mm base radius) and Type 1 specimen size (length of 80 mm, width of 10 mm, and thickness of 4 mm). Specimens are cut from the center of a multi-purpose bar using a single tooth milling machine. The testing temperature is 23° C., −30° F., or −40° F. as reported below.

Unnotched Charpy Impact Strength: Unnotched Charpy properties are tested according to ISO Test No. 180 (technically equivalent to ASTM D256). The test is run using a Type 1 specimen (length of 80 mm, width of 10 mm and thickness of 4 mm). Specimens are cut from the center of a multi-purpose bare using a single tooth milling machine. The testing temperature is 23° C.

Izod Notched Impact Strength: Notched Izod properties are tested according to ISO Test No. 180 (technically equivalent to ASTM D256, Method A). This test is run using a Type A notch. Specimens are cut from the center of a multi-purpose bar using a single tooth milling machine. The testing temperature is 23° C.

Density and Specific Gravity: Density was determined according to ISO Test No. 1183 (technically equivalent to ASTM D792). The specimen was weighed in air then weighed when immersed in distilled water at 23° C. using a sinker and wire to hold the specimen completely submerged as required.

Vicat softening temperature: Vicat Softening temperature was determined according to method A, with a load of 10 N and according to method B with a load of 50 N as described in ISO Test No. 306 (technically equivalent to ASTM D1525), both of which utilized a heating rate of 50 K/h.

Water absorption was determined according to ISO Test No. 62. The test specimens are immersed in distilled water at 23° C. until the water absorption essentially ceases (23° C./sat).

Complex viscosity: Complex viscosity is determined by a Low shear sweep (ARES) utilizing an ARES-G2 (TA Instruments) testing machine equipped with 25 mm SS parallel plates and using TRIOS software. A dynamic strain sweep was performed on a pellet sample prior to the frequency sweep, in order to find LVE regime and optimized testing condition. The strain sweep was done from 0.1% to 100%, at a frequency 6.28 rad/s. The dynamic frequency sweep for each sample was obtained from 500 to 0.1 rad/s, with strain amplitude of 3%. The gap distance was kept at 1.5 mm for pellet samples. The temperature was set at 310° C. for all samples.

Melt strength and melt elongation is performed on ARES-G2 Equipped EVF Fixture. The flame bar sample was cut as shown in FIG. 18. The same area of flame bar was used for each run, in order to keep the crystallinity of test sample same and thus to minimize the variation between replicates. A transient strain was applied to each sample at 0.2/s rate. At least triplicate run was done for each sample to obtain a representative curve.

Permeation Resistance: The fuel permeation studies were performed on samples according to SAE Testing Method No. J2665. For all samples, stainless-steel cups were used. Injection molded plaques with a diameter of 3 inches (7.6 centimeters) were utilized as test samples. The thickness of each sample was measured in 6 different areas. An O-ring Viton® fluoroelastomer was used as a lower gasket between cup flange and sample (Purchased from McMaster-Carr, cat#9464K57, A75). A flat Viton® fluoroelastomer (Purchased from McMaster-Carr, cat#86075K52, 1/16″ thickness, A 75) was die-cut to 3 inch (7.6 cm) OD and 2.5 inch (6.35 cm) ID, and used as the upper gasket between the sample and the metal screen. The fuel, about 200 ml, was poured into the cup, the cup apparatus was assembled, and the lid was finger-tightened. This was incubated in a 40° C. oven for 1 hour, until the vapor pressure equilibrated and the lid was tightened to a torque 15 in-lb. The fuel loss was monitored gravimetrically, daily for the first 2 weeks followed by twice a week for the rest of the testing period. A blank run was done in the same manner with an aluminum disk (7.6 cm diameter, 1.5 mm thickness) and the result was subtracted from the samples. All samples were measured in duplicate. The normalized permeation rate was calculated following an equilibration period. The permeation rate for each sample was obtained from the slope of linear regression fitting of daily weight loss (gm/day). The normalized permeation rate was calculated by dividing the permeation rate by the effective permeation area and multiplying by average thickness of specimen. The average permeation rates are reported.

Salt resistance: zinc chloride resistance was tested by use of tensile bar samples immersed in a 50% aqueous solution (by weight) of zinc chloride for 200 h at 23±2° C. Charpy notched impact test was then carried out at −30° C. calcium chloride resistance was tested by use of tensile bar samples immersed in a 50% aqueous solution (by weight) of calcium chloride for 200 h at 60±2° C. and 200 h out of solution at 60±2° C. Charpy notched impact test was then carried out at −30° C.

Hydrocarbon volume uptake: Absorption and diffusion testing was performed using the tab ends cut from supplied tensile bars. Each material was immersed in Brent crude oil, hydrocarbon/water mixture (and in a one-off test to hydrocarbon only). Rates and amounts of liquid absorbed were measured. The hydrocarbon liquid mixture had the following composition:

Volume percent (%) Composition 10 Distilled water 60 70% heptane, 20% cyclohexane and 10% Toluene balance Nitrogen

All exposure testing was conducted at 130° C. for a period of two weeks utilizing an air-circulating oven, air having been removed from the test vessel by purging with nitrogen; the test being conducted at vapor pressure.

Example 1

Materials utilized to form the compositions included the following:

Polyarylene sulfide: Fortron® 0214 linear polyphenylene sulfide available from Ticona Engineering Polymers of Florence, Ky.

Impact Modifier: LOTADER® AX8840—a random copolymer of ethylene and glycidyl methacrylate available from Arkema, Inc.

Crosslinking Agent: Terephthalic Acid

Disulfide: 2,2-dithiodibenzoic acid

Lubricant: Glycolube® P available from Lonza Group Ltd.

Materials were melt mixed using a Coperion co-rotating, fully-intermeshing, twin-screw extruder with an overall L/D of 40 and ten temperature control zones including one at the die. A high shear screw design was used to compound the additives into a resin matrix. The polyarylene sulfide, impact modifier and lubricant were fed to the main feed throat in the first barrel by means of a gravimetric feeder. Upon melting and mixing of the above ingredients, the disulfide was fed using a gravimetric feeder at barrel 6. Materials were further mixed then extruded through a strand die. The strands were water-quenched in a bath to solidify and granulated in a pelletizer.

Compositions of the samples are provided in Table 1, below. Amounts are provided as weight percentages based upon the weight of the sample.

TABLE 1 Component Addition Point Sample 1 Sample 2 Lubricant main feed 0.3 0.3 Disulfide barrel 6 1.0 Impact Modifier main feed 25.0 25.0 Polyarylene Sulfide main feed 74.7 73.7 Total 100.0 100.0

Following formation, samples were tested for a variety of physical characteristics. Results are provided in Table 2, below.

TABLE 2 Sample 1 Sample 2 Melt Viscosity (poise) 3328 4119 Tensile Modulus (MPa) 1826 1691 Tensile Break Stress (MPa) 43.73 44.98 Tensile Break Strain (%) 96.37 135.12 Std. Dev. 39.07 34.40 Notched Charpy Impact 61.03 53.00 Strength at 23° C. (kJ/m²)

Samples were annealed at 230° C. for 2 hours and re-tested for physical characteristics. Results are provided in Table 3, below.

TABLE 3 Sample 1 Sample 2 Tensile Modulus (MPa) 1994.00 1725.00 Tensile Break Stress (MPa) 45.04 45.20 Tensile Break Strain (%) 58.01 73.76 Std. Dev. 6.60 4.78

As can be seen, Sample 2 exhibited better tensile elongation and lower modulus before and after annealing. However, no improvement in impact strength was seen, which is believed to be due to a chain scission reaction between the disulfide and the polypropylene sulfide.

Example 2

Materials as described in Example 1 were melt mixed using a Coperion co-rotating, fully-intermeshing, twin-screw extruder with an overall L/D of 40 and ten temperature control zones including one at the die. A high shear screw design was used to compound the additives into a resin matrix. The polyarylene sulfide, impact modifier and lubricant were fed to the main feed throat in the first barrel by means of a gravimetric feeder. The disulfide was fed using a gravimetric feeder at various locations in the extruder; at the main feed throat, at barrel 4 and barrel 6. The crosslinking agent was fed at barrel 6. Materials were further mixed then extruded through a strand die. The strands were water-quenched in a bath to solidify and granulated in a pelletizer.

Comparative Samples 3 and 4 were formed of the same composition and compounded by use of a different screw design.

TABLE 4 Addition Point 3 4 5 6 7 8 9 10 Lubricant main feed 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 Crosslinking barrel 6 — — 0.5 1.0 1.0 0.5 0.5 0.5 Agent Disulfide main feed — — — — — 0.30 — — Disulfide barrel 4 — — — — — — 0.3 — Disulfide barrel 6 — — — — — — — 0.3 Impact main feed 15.0 15.0 15.0 15.0 10.0 15.0 15.0 15.0 Modifier Polyarylene main feed 84.7 84.7 84.2 83.7 88.7 83.9 83.9 83.9 Sulfide Total 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0

Following formation, tensile bars were formed and tested for a variety of physical characteristics. Results are provided in Table 5, below.

TABLE 5 Sample Sample 3 Sample 4 Sample 5 Sample 6 Sample 7 Sample 8 Sample 9 10 Melt 2423 — 2659 2749 2067 2349 2310 2763 Viscosity (poise) Density — 1.28 — 1.25 — — — — (g/cm³) Tensile 2076 2800 2177 2207 2551 1845 2185 2309 Modulus (MPa) Tensile 46.13 — 45.40 48.27 51.71 46.47 47.16 47.65 Break Stress (MPa) Tensile 33.68 25 43.97 35.94 26.90 47.51 40.85 63.85 Break Strain (%) Elongation 5.17 5 5.59 7.49 4.5 11.78 6.94 7.00 at Yield (%) Yield Stress 51.07 52 50.76 51.62 59.63 51.07 52.56 51.88 (MPa) Notched 22.30 30 23.90 39.40 14.80 12.50 19.70 39.90 Charpy Impact Strength at 23° C. (kJ/m²) Notched 7.8 7 — 10 — — — 10.8 Charpy Impact Strength at −30° C. (kJ/m²) DTUL (° C.) — 100 — 102 — — — — Melt Temp. 280 280 280 280 280 280 280 280 (° C.) Water — 0.05 — 0.05 — — — — absorption (%) Hydrocarbon 16 — — — — — — — volume uptake (%)

Samples were annealed at 230° C. for 2 hours and re-tested for physical characteristics. Results are provided in Table 6, below.

TABLE 6 Sample Sample 3 Sample 4 Sample 5 Sample 6 Sample 7 Sample 8 Sample 9 10 Tensile 2383 — 2339 2279 2708 2326 2382 2491 Modulus (MPa) Tensile 52.70 — 53.96 53.11 61.10 56.74 54.81 55.25 Break Stress (MPa) Tensile 29.42 — 20.97 35.76 20.34 31.37 41.23 49.03 Break Strain (%) Std. 6.84 — 6.95 6.66 5.40 2.83 2.65 3.74 Dev.

As can be seen, the highest tensile elongation and highest impact strength were observed for Sample 10, which includes both the crosslinking agent and the disulfide added at the same point downstream during processing.

FIG. 19 illustrates the relationship of notched Charpy impact strength over temperature change for Sample 3 and for Sample 6. As can be seen, the polyarylene sulfide composition of Sample 6 exhibits excellent characteristics over the entire course of the temperature change, with a higher rate of increase in impact strength with temperature change as compared to the comparison material.

FIG. 20 is a scanning electron microscopy image of the polyarylene sulfide used in forming the sample 3 composition (FIG. 20A) and the Sample 6 composition (FIG. 20B). As can be seen, there is no clear boundary between the polyarylene sulfide and the impact modifier in the composition of FIG. 20B.

Tensile bar test specimens of samples 3, 6, and 10 were immersed in 10 wt. % sulfuric acid for 500 hours at either 40° C. or 80° C. Tensile properties and impact properties were measured before and after the acid exposure. Results are summarized in Table 7 below.

TABLE 7 Sample 3 Sample 6 Sample 10 Initial properties Tensile Modulus (MPa) 2076 2207 2309 Tensile Break Stress (MPa) 46.13 48.27 47.65 Tensile Break Strain (%) 33.68 35.94 63.85 Charpy notched impact 22.30 39.40 39.90 strength at 23° C. (kJ/m²) Properties after 500 hours exposure in sulfuric acid at 40° C. Tensile Modulus (MPa) 2368 2318 2327 Tensile Break Stress (MPa) 48.83 48.48 48.53 Tensile Break Strain (%) 10.99 28.28 30.05 Charpy notched impact 18.4 33.6 35.9 strength at 23° C. (kJ/m²) Loss in Charpy notched impact 18 15 15 strength (%) Properties after 500 hour exposure in sulfuric acid at 80° C. Tensile Modulus (MPa) 2341 2356 2354 Tensile Break Stress (MPa) 49.61 48.04 48.86 Tensile Break Strain (%) 10.60 19.88 26.32 Charpy notched impact 9.2 31.0 34.0 strength at 23° C. (kJ/m²) Loss in Charpy notched impact 59 21 15 strength (%)

The results in the change in Charpy notched impact strength over time during exposure to the acid solution at an elevated temperature are illustrated in FIG. 21. As can be seen, the relative loss of strength of samples 6 and 10 is much less than the comparison sample.

Example 3

Materials as described in Example 1 were melt mixed using a Coperion co-rotating, fully-intermeshing, twin-screw extruder with an overall L/D of 40 and ten temperature control zones including one at the die. A high shear screw design was used to compound the additives into a resin matrix. The polyarylene sulfide, impact modifier and lubricant were fed to the feed throat in the first barrel by means of a gravimetric feeder. The crosslinking agent was fed using a gravimetric feeder at the main feed throat and at barrel 6. Materials were further mixed then extruded through a strand die. The strands were water-quenched in a bath to solidify and granulated in a pelletizer.

Compositions of the samples are provided in Table 8, below. Amounts are provided as weight percentages based upon the weight of the sample.

TABLE 8 Addition Sample Sample Sample Sample Component Point 11 12 13 14 Lubricant main 0.3 0.3 0.3 0.3 feed Crosslinking main — 0.5 1.0 — Agent feed Crosslinking barrel 6 — — — 1.0 Agent Impact main 15.0 15.0 15.0 15.0 Modifier feed Polyarylene main 84.7 84.2 83.7 83.7 Sulfide feed Total 100.0 100.0 100.0 100.0

Following formation, tensile bars formed of the samples were tested for a variety of physical characteristics. Results are provided in Table 9, below.

TABLE 9 Sample Sample Sample Sample 11 12 13 14 Melt Viscosity (poise) 2649 2479 2258 3778 Tensile Modulus (MPa) 2387 2139 2150 1611 Tensile Break Stress 46.33 49.28 51.81 42.44 (MPa) Tensile Break Strain 24.62 22.60 14.45 53.62 (%) Std. Dev. 9.19 1.51 2.23 1.90 Notched Charpy 27.50 8.50 6.00 39.30 Impact Strength at 23° C. (kJ/m²) Std. Dev. 2.7 1.10 0.60 2.10

As can be seen, upstream feed of the crosslinking agent decreased the impact properties of the composition, while downstream feed increased the tensile elongation by 118% and room temperature impact strength by 43%.

Example 4

Materials as described in Example 1 were melt mixed using a Coperion co-rotating, fully-intermeshing, twin-screw extruder with an overall L/D of 40 and ten temperature control zones including one at the die. A high shear screw design was used to compound the additives into a resin matrix. The polyarylene sulfide, impact modifier and lubricant were fed to the feed throat in the first barrel by means of a gravimetric feeder. The crosslinking agent was fed using a gravimetric feeder at barrel 6. Materials were further mixed then extruded through a strand die. The strands were water-quenched in a bath to solidify and granulated in a pelletizer.

Compositions of the samples are provided in Table 10, below. Amounts are provided as weight percentages based upon the weight of the sample.

TABLE 10 Addition Sample Sample Sample Sample Component Point 15 16 17 18 Lubricant main 0.3 0.3 0.3 0.3 feed Crosslinking barrel 6 1.0 1.7 1.0 1.7 Agent Impact main 25.0 25.0 15.0 15.0 Modifier feed Polyarylene main 73.7 73.0 83.7 83.0 Sulfide feed Total 100.0 100.0 100.0 100.0

Following formation, tensile bars formed of the samples were tested for a variety of physical characteristics. Results are provided in Table 11, below.

TABLE 11 Sample Sample Sample Sample 15 16 17 18 Melt Viscosity (poise) 4255 4198 2522 2733 Density (g/cm³) 1.2 — — — Tensile Modulus (MPa) 1582.00 1572.00 2183.00 2189.00 Tensile Break Stress 45.59 46.29 48.98 49.26 (MPa) Tensile Break Strain 125.92 116.40 66.13 48.24 (%) Std. Dev. 19.79 9.97 15.36 7.80 Elongation at Yield (%) 23 — — — Yield Stress (MPa) 42 — — — Flex Modulus (MPa) 1946.00 1935.00 2389.00 2408.00 Flexural Stress @3.5% 48.30 48.54 68.55 68.12 (MPa) Notched Charpy 55.60 51.80 43.60 19.10 Impact Strength at 23° C. (kJ/m²) Std. Dev. 1.00 1.40 1.50 1.50 Notched Charpy 13 — — — Impact Strength at −30° C. (kJ/m²) Notched Charpy 13.30 12.10 11.26 8.70 Impact Strength at −40° C. (kJ/m²) Std. Dev. 1.50 0.90 0.26 0.50 DTUL (1.8 MPa) (° C.) 97.20 97.60 101.70 100.90 Water absorption (%) 0.07 — — —

Example 5

Materials as described in Example 1 were utilized except for the polyarylene sulfide, which was Fortron® 0320 linear polyphenylene sulfide available from Ticona Engineering Polymers of Florence, Ky. Materials were melt mixed using a Coperion co-rotating, fully-intermeshing, twin-screw extruder with an overall L/D of 40 and ten temperature control zones including one at the die. A high shear screw design was used to compound the additives into a resin matrix. The polyarylene sulfide and impact modifier were fed to the feed throat in the first barrel by means of a gravimetric feeder. The crosslinking agent was fed using a gravimetric feeder at barrel 6. Materials were further mixed then extruded through a strand die. The strands were water-quenched in a bath to solidify and granulated in a pelletizer.

Compositions of the samples are provided in Table 12, below. Amounts are provided as weight percentages based upon the weight of the sample.

TABLE 12 Addition Sample Sample Sample Sample Sample Component Point 19 20 21 22 23 Crosslinking barrel 6 — — — 0.1 0.2 Agent Impact main — 1.5 3.0 1.5 3.0 Modifier feed Polyarylene main 100.0 98.5 97.0 98.4 96.8 Sulfide feed Total 100.0 100.0 100.0 100.0 100.0

Following formation, tensile bars formed of the samples were tested for a variety of physical characteristics. Results are provided in Table 13, below.

TABLE 13 Sample Sample Sample Sample Sample 19 20 21 22 23 Melt Viscosity (poise) 2435 2684 2942 2287 1986 Tensile Modulus (MPa) 3208 3207 3104 3245 3179 Tensile Break Stress 67.20 72.94 59.06 63.95 60.80 (MPa) Tensile Break Strain 2.46 4.54 11.96 6.31 11.40 (%) Std. Dev. 0.32 1.11 1.24 2.25 3.53 Flex Modulus (MPa) 3103.00 3173.00 3031.00 3284.00 3156.00 Flexural Stress @3.5% 105.76 104.74 100.21 109.09 104.81 (MPa) Notched Izod Impact 2.90 5.20 5.60 4.10 4.30 Strength at 23° C. (kJ/m²) Std. Dev. 0.40 0.40 0.40 0.20 0.20 DTUL (1.8 MPa) (° C.) 105.60 104.00 103.70 104.20 104.80

Example 6

Materials utilized to form the compositions included the following:

Polyarylene sulfide: Fortron® 0214 linear polyphenylene sulfide available from Ticona Engineering Polymers of Florence, Ky. Impact Modifier: LOTADER® 4720—a random terpolymer of ethylene, ethyl acrylate and maleic anhydride available from Arkema, Inc.

Crosslinking Agent: Hydroquinone

Lubricant: Glycolube® P available from Lonza Group Ltd.

Materials were melt mixed using a Coperion co-rotating, fully-intermeshing, twin-screw extruder with an overall L/D of 40 and ten temperature control zones including one at the die. A high shear screw design was used to compound the additives into a resin matrix. The polyarylene sulfide, impact modifier and lubricant were fed to the main feed throat in the first barrel by means of a gravimetric feeder. Upon melting and mixing of the above ingredients, the crosslinking agent was fed using a gravimetric feeder at the main feed for samples 24 and 25 and at barrel 6 for samples 26 and 27. Materials were further mixed then extruded through a strand die. The strands were water-quenched in a bath to solidify and granulated in a pelletizer.

Compositions of the samples are provided in Table 14, below. Amounts are provided as weight percentages based upon the weight of the sample.

TABLE 14 Addition Sample Sample Sample Sample Sample Component Point 24 25 26 27 28 Lubricant main feed 0.3 0.3 0.3 0.3 0.3 Crosslinking barrel 6 — — — 0.1 0.2 Agent Crosslinking main feed — 0.1 0.2 — — Agent Impact main feed 15.0 15.0 15.0 15.0 15.0 Modifier Polyarylene main feed 84.7 84.6 84.5 84.6 84.5 Sulfide Total 100.0 100.0 100.0 100.0 100.0

Following formation, samples were tested for a variety of physical characteristics. Results are provided in Table 15, below.

TABLE 15 Sample Sample Sample Sample Sample 24 25 26 27 28 Melt Viscosity 2435 2797 3251 2847 2918 (poise) Tensile Modulus 2222 2164 2163 2184 2145 (MPa) Tensile Break 52.03 45.17 46.53 45.47 46.39 Stress (MPa) Tensile Break 36.65 50.91 63.39 38.93 41.64 Strain (%) Std. Dev. 9.09 14.9 11.88 7.62 10.42 Elongation at Yield 5.75 5.49 5.76 5.53 5.70 (%) Yield Stress (MPa) 52.03 50.21 50.77 51.39 50.85 Flexural Modulus 2358.00 2287.00 2286.00 2305.00 2281.00 (MPa) Flexural Stress 70.51 68.25 68.03 69.23 68.23 @3.5% (MPa) Notched Charpy 29.80 44.60 50.60 42.30 45.90 Impact Strength at 23° C. (kJ/m²) Std. Dev. 4.10 2.40 1.90 1.90 1.60 Notched Charpy 5.90 9.30 11.00 9.60 9.80 Impact Strength at −40° C. (kJ/m²) Std. Dev. 1.00 0.90 1.20 0.80 1.30 DTUL (1.8 MPa) 99.10 93.90 98.20 100.10 99.00 (° C.)

Example 7

Materials utilized to form the compositions included the following:

Polyarylene sulfide:

PPS1—Fortron® 0203 linear polyphenylene sulfide available from Ticona Engineering Polymers of Florence, Ky. PPS2—Fortron®0205 linear polyphenylene sulfide available from Ticona Engineering Polymers of Florence, Ky. PPS3—Fortron®0320 linear polyphenylene sulfide available from Ticona Engineering Polymers of Florence, Ky. Impact Modifier: LOTADER® AX8840—a random copolymer of ethylene and glycidyl methacrylate available from Arkema, Inc.

Crosslinking Agent: Terephthalic Acid

Lubricant: Glycolube® P available from Lonza Group Ltd.

Materials were melt mixed using a Coperion co-rotating, fully-intermeshing, twin-screw extruder with an overall L/D of 40 and ten temperature control zones including one at the die. A high shear screw design was used to compound the additives into a resin matrix. The polyarylene sulfide, impact modifier and lubricant were fed to the main feed throat in the first barrel by means of a gravimetric feeder. Upon melting and mixing of the above ingredients, the crosslinking agent was fed using a gravimetric feeder at barrel 6. Materials were further mixed then extruded through a strand die. The strands were water-quenched in a bath to solidify and granulated in a pelletizer.

Compositions of the samples are provided in Table 16, below. Amounts are provided as weight percentages based upon the weight of the sample.

TABLE 16 Addition Sample Sample Sample Sample Sample Sample Component Point 29 30 31 32 33 34 Lubricant main 0.3 0.3 0.3 0.3 0.3 0.3 feed Crosslinking barrel 6 1.0 1.0 1.0 Agent Impact main 15.0 15.0 15.0 15.0 15.0 15.0 Modifier feed PPS1 main 84.7 83.7 feed PPS2 main 84.7 83.7 feed PPS3 main 84.7 83.7 feed Total 100.0 100.0 100.0 100.0 100.0 100.0

Following formation, samples were tested for a variety of physical characteristics. Results are provided in Table 17, below.

TABLE 17 Sample Sample Sample Sample Sample Sample 29 30 31 32 33 34 Tensile 2292 2374 2250 2427 2130 2285 Modulus (MPa) Tensile Break 50.92 50.18 49.18 53.22 48.01 48.08 Stress (MPa) Tensile Break 5.79 2.84 23.79 34.73 23.55 45.42 Strain (%) Std. Dev. 0.99 0.18 11.96 4.01 18.57 18.94 Flexural 2279.00 2382.00 2257.00 2328.00 2292.00 2294.00 Modulus (MPa) Flexural Stress 71.11 74.94 69.72 72.39 67.95 68.95 @3.5% (MPa) Notched 5.70 3.70 9.10 12.80 19.40 45.40 Charpy Impact Strength at 23° C. (kJ/m²) Std. Dev. 0.90 0.70 0.80 1.00 2.70 7.70 Notched 3.00 2.50 5.10 5.00 5.10 8.00 Charpy Impact Strength at −40° C. (kJ/m²) Std. Dev. 0.70 0.30 0.60 0.30 0.40 1.00 DTUL 101.00 105.50 100.00 102.90 99.90 100.40 (1.8 MPa) (° C.)

Example 8

Materials utilized to form the compositions included the following:

Polyarylene sulfide: Fortron® 0214 linear polyphenylene sulfide available from Ticona Engineering Polymers of Florence, Ky. Impact Modifier: LOTADER® AX8840—a random copolymer of ethylene and glycidyl methacrylate available from Arkema, Inc.

Crosslinking Agent: Terephthalic Acid

Lubricant: Glycolube® P available from Lonza Group Ltd.

Materials were melt mixed using a Coperion co-rotating, fully-intermeshing, twin-screw extruder with an overall L/D of 40 and ten temperature control zones including one at the die. A high shear screw design was used to compound the additives into a resin matrix. The polyarylene sulfide, impact modifier and lubricant were fed to the main feed throat in the first barrel by means of a gravimetric feeder. Upon melting and mixing of the above ingredients, the crosslinking agent was fed using a gravimetric feeder at barrel 6. Materials were further mixed then extruded through a strand die. The strands were water-quenched in a bath to solidify and granulated in a pelletizer.

Compositions of the samples are provided in Table 18, below. Amounts are provided as weight percentages based upon the weight of the sample.

TABLE 18 Addition Sample Sample Sample Sample Sample Sample Component Point 35 36 37 38 39 40 Lubricant main 0.3 0.3 0.3 0.3 0.3 0.3 feed Crosslinking barrel 6 0.75 1.25 1.75 Agent Impact main 15.0 15.0 25.0 25.0 35.0 35.0 Modifier feed Polyarylene main 84.7 83.95 74.70 73.45 64.70 62.95 Sulfide feed Total 100.0 100.0 100.0 100.0 100.0 100.0

Following formation, samples were tested for a variety of physical characteristics. Results are provided in Table 19, below. Sample 39 was not injection moldable.

TABLE 19 Sample Sample Sample Sample Sample Sample 35 36 37 38 39 40 Melt 2323 2452 2955 3821 2025 5462 Viscosity (poise) Tensile 2281 2298 2051 1721 — 1045 Modulus (MPa) Tensile Break 47.09 49.09 47.29 46.18 — 39.81 Stress (MPa) Tensile Break 28.92 36.42 97.33 110.36 — 96.76 Strain (%) Std. Dev. 6.35 3.13 53.94 8.40 — 1.77 Elongation 5.28 8.58 36.00 108.19 — 95.77 at Yield (%) Yield Stress 52.42 53.92 46.50 46.76 — 40.43 (MPa) Flexural 2388.00 2349.00 2210.00 1750.00 — 1209.00 Modulus (MPa) Flexural Stress 71.52 71.70 63.15 50.52 — 34.41 @3.5% (MPa) Notched 35.15 38.40 57.00 52.70 — 52.10 Charpy Impact Strength at 23° C. (kJ/m²) Std. Dev. 6.22 1.50 1.40 3.40 — 2.10 Notched 8.20 10.70 8.70 18.10 — 14.10 Charpy Impact Strength at −30° C. (kJ/m²) Std. Dev. 1.50 1.60 0.20 0.90 — 0.80 Notched 7.26 9.20 8.00 16.80 — 12.47 Charpy Impact Strength at −40° C. (kJ/m²) Std. Dev. 1.54 2.30 0.60 0.40 — 0.92 DTUL 99.90 103.60 98.10 99.30 — 92.70 (1.8 MPa) (° C.) Water — — — — — 0.1 absorption (%)

Example 9

Materials utilized to form the compositions included the following:

Polyarylene sulfide: Fortron® 0214 linear polyphenylene sulfide available from Ticona Engineering Polymers of Florence, Ky.

Impact Modifier: LOTADER® AX8840—a random copolymer of ethylene and glycidyl methacrylate available from Arkema, Inc.

Crosslinking Agent: Terephthalic Acid

Lubricant: Glycolube® P available from Lonza Group Ltd.

Materials were melt mixed using a Coperion co-rotating, fully-intermeshing, twin-screw extruder with an overall L/D of 40 and ten temperature control zones including one at the die. A high shear screw design was used to compound the additives into a resin matrix. The polyarylene sulfide, impact modifier and lubricant were fed to the main feed throat in the first barrel by means of a gravimetric feeder. Upon melting and mixing of the above ingredients, the crosslinking agent was fed using a gravimetric feeder at barrel 6. Materials were further mixed then extruded through a strand die. The strands were water-quenched in a bath to solidify and granulated in a pelletizer.

Compositions of the samples are provided in Table 20, below. Amounts are provided as weight percentages based upon the weight of the sample.

TABLE 20 Addition Sample Sample Sample Sample Component Point 41 42 43 44 Lubricant main 0.3 0.3 0.3 0.3 feed Crosslinking barrel 6 1.0 1.1 1.25 1.25 Agent Impact main 15 20 25 30 Modifier feed Polyarylene main 83.7 78.6 73.45 68.45 Sulfide feed Total 100.0 100.0 100.0 100.0

Following formation, samples were tested for a variety of physical characteristics. Results are provided in Table 21, below.

TABLE 21 Sample Sample Sample Sample 41 42 43 44 Specific Gravity 1.25 1.20 1.15 1.20 (g/cm³) Tensile Modulus 2200 1600 1200 1700 (MPa) (50 mm/min) Tensile Break 50 42 40 46 Strength (MPa) (50 mm/min) Elongation at 40 100 90 75 Break (%) (50 mm/min) Yield Stress (MPa) 55 42 40 48 (50 mm/min) Yield Strain (%) 9 25 90 15 (50 mm/min) Flexural Modulus 2200 1700 1300 1900 (MPa) Flexural Strength 68 50 40 56 @3.5% (MPa) Notched Charpy 40 55 50 50 Impact Strength at 23° C. (kJ/m²) Notched Charpy 10 24 20 20 Impact Strength at −30° C. Unnotched Charpy Not Not Not Not Impact Strength at broken broken broken broken 23° C. DTUL (1.8 MPa) 102 100 95 100 (° C.) Water absorption 0.05 0.07 0.1 0.05 (%) Vicat softening 270 270 270 270 temp. (A10N, ° C.) Vicat softening 200 160 110 180 temp. (B50N, ° C.) Complex viscosity 79.994 289.27 455.19 — (0.1 rad/sec, 310° C.) (kPa/sec) Hydrocarbon 14 23 — 19 volume uptake (%)

Samples 41, 42, and 43 were tested to determine complex viscosity as well as melt strength and melt elongation as a function of Hencky strain. As a comparative material, Sample 3 as described in Example 2 was utilized. Samples 41, 42 and 43 were done at 310° C. and sample 3 was done at 290° C. Results are shown in FIG. 22, FIG. 23, and FIG. 24.

Example 10

Samples 41, 42, and 43 described in Example 9 were tested to determine permeation of various fuels including CE10 (10 wt. % ethanol, 45 wt. % toluene, 45 wt. % iso-octane), CM15A (15 wt. % methanol and 85 wt. % oxygenated fuel), and methanol. Sample No. 4 described in Example 2 was utilized as a comparison material. Two samples of each material were tested.

Table 22, below provides the average sample thickness and effective area for the samples tested with each fuel.

TABLE 22 Average Sample Sample Thickness (mm) Effective area (m²) CE10 Aluminum blank-1 1.50 0.00418 Aluminum blank-2 1.50 0.00418 Sample No. 4-1 1.47 0.00418 Sample No. 4-2 1.45 0.00418 Sample No. 41-1 1.47 0.00418 Sample No. 41-2 1.49 0.00418 Sample No. 42-1 1.47 0.00418 Sample No. 42-2 1.46 0.00418 Sample No. 43-1 1.45 0.00418 Sample No. 43-2 1.47 0.00418 CM15A Aluminum blank-1 1.50 0.00418 Aluminum blank-2 1.50 0.00418 Sample No. 4-1 1.48 0.00418 Sample No. 4-2 1.49 0.00418 Sample No. 41-1 1.49 0.00418 Sample No. 41-2 1.50 0.00418 Sample No. 42-1 1.47 0.00418 Sample No. 42-2 1.48 0.00418 Sample No. 43-1 1.46 0.00418 Sample No. 43-2 1.47 0.00418 Methanol Aluminum blank-1 1.50 0.00418 Aluminum blank-2 1.50 0.00418 Sample No. 4-1 1.49 0.00418 Sample No. 4-2 1.49 0.00418 Sample No. 41-1 1.49 0.00418 Sample No. 41-2 1.51 0.00418 Sample No. 42-1 1.48 0.00418 Sample No. 42-2 1.47 0.00418 Sample No. 43-1 1.47 0.00418 Sample No. 43-2 1.48 0.00418

The daily weight losses for each material and each fuel are shown in FIGS. 25-27. Specifically, FIG. 25 shows the daily weight loss for the samples during the permeation test of CE10, FIG. 26 shows the daily weight loss for the samples during the permeation test of CM15A, and FIG. 27 shows the daily weight loss for the samples during the permeation test of methanol.

The average permeation rates for each sample with each fuel are provided in Table 23. Note that Sample No. 43 takes a longer time to arrive at equilibrium, so the linear regression fitting was generated based on data between days 42 and 65 for this material, while the linear regress fitting was generated for the other materials between days 32 and 65. For methanol, the linear regression fitting was generated based on data between days 20 and 65, but with Sample No. 604, the methanol linear regression fitting was generated based on data between days 30 and 65. Some samples show negative permeability, which is because the weight loss of the sample was lower than that of the aluminum blank.

TABLE 23 Average Normalized Normalized Perm- Average permeation permeation eation- Permeation- (g-mm/ (g-mm/ 3 mm 3 mm Sample day-m²) day-m²) thickness thickness CE10 Sample No. 4-1 0.06 0.05 ± 0.01 0.02 0.02 ± 0   Sample No. 4-2 0.05 0.02 Sample No. 41-1 0.07 0.04 ± 0.04 0.02 0.01 ± 0.01 Sample No. 41-2 0.01 0.00 Sample No. 42-1 0.06 0.06 ± 0   0.02 0.02 ± 0   Sample No. 42-2 0.06 0.02 Sample No. 43-1 2020 2.51 ± 0.43 0.73 0.84 ± 0.14 Sample No. 43-2 2.81 0.94 CM15A Sample No. 4-1 0.49 0.18 ± 0.44 0.16 0.06 ± 0.15 Sample No. 4-2 −0.13 −0.04 Sample No. 41-1 0.50 0.11 ± 0.55 0.17 0.04 ± 0.18 Sample No. 41-2 −0.27 −0.09 Sample No. 42-1 −0.13 0.27 ± 0.58 −0.04 0.09 ± 0.19 Sample No. 42-2 0.68 0.23 Sample No. 43-1 2.04 2.29 ± 0.35 0.68 0.76 ± 0.12 Sample No. 43-2 2.53 0.84 Methanol Sample No. 4-1 0.37 0.25 ± 0.18 0.12 0.08 ± 0.06 Sample No. 4-2 0.13 0.04 Sample No. 41-1 0.02 0.05 ± 0.05 0.01 0.02 ± 0.02 Sample No. 41-2 0.08 0.03 Sample No. 42-1 0.28 0.25 ± 0.05 0.09 0.08 ± 0.02 Sample No. 42-2 0.21 0.07 Sample No. 43-1 0.27 0.41 ± 0.2  0.09 0.14 ± 0.07 Sample No. 43-2 0.55 0.18 The error was derived from the standard deviation of duplicates in each sample.

These and other modifications and variations of the present invention may be practiced by those of ordinary skill in the art, without departing from the spirit and scope of the present invention. In addition, it should be understood that aspects of the various embodiments may be interchanged both in whole or in part. Furthermore, those of ordinary skill in the art will appreciate that the foregoing description is by way of example only, and is not intended to limit the invention so further described in such appended claims. 

What is claimed is:
 1. A pipe section, comprising: a hollow body formed from a polymer material, the hollow body having an inner surface and an outer surface, the inner surface defining an interior; a barrier layer surrounding and unbonded from the hollow body, the barrier layer having an inner surface and an outer surface, the barrier layer formed from a continuous fiber reinforced thermoplastic material.
 2. The pipe section of claim 1, wherein the barrier layer is a tape.
 3. The pipe section of claim 2, wherein the tape is wrapped generally helically around the hollow body with respect to a longitudinal axis of the hollow body.
 4. The pipe section of claim 1, wherein the continuous fibers are generally unidirectional.
 5. The pipe section of claim 1, wherein the hollow body is formed from a thermoplastic material.
 6. The pipe section of claim 1, wherein the continuous fibers are carbon fibers.
 7. The pipe section of claim 1, wherein the continuous fibers are glass fibers.
 8. The pipe section of claim 1, wherein the continuous fibers are aramid fibers.
 9. The pipe section of claim 1, wherein the thermoplastic material is a polyarylene sulfide composition.
 10. The pipe section of claim 9, wherein the polyarylene sulfide composition comprises a polyarylene sulfide and a crosslinked impact modifier.
 11. The pipe section of claim 1, wherein the barrier layer is a plurality of barrier layers.
 12. A method for forming a pipe section, the method comprising surrounding a hollow body with a barrier layer such that the barrier layer is in contact with and unbonded from an outer surface of the hollow body, the barrier layer formed from a continuous fiber reinforced thermoplastic material.
 13. The method of claim 12, wherein the surrounding step comprises wrapping the barrier layer generally helically around the hollow body with respect to a longitudinal axis of the hollow body.
 14. The method of claim 12, wherein the barrier layer is a tape formed from the continuous fiber reinforced thermoplastic material.
 15. The method of claim 12, further comprising forming the tape, the forming step comprising: flowing a thermoplastic resin through a manifold assembly of a die, the manifold assembly comprising a plurality of branched runners; coating at least one fiber roving with the resin; and traversing the coated roving through an impregnation zone of the die to impregnate the roving with the resin. 